Corrosion inhibitor composition and methods of inhibiting corrosion during acid pickling

ABSTRACT

A corrosion inhibitor composition, which includes i) an aqueous alcohol base fluid, ii) a mixture of at least three polysaccharides selected from carboxymethyl cellulose, gum arabic, pectin, a salt of alginic acid, chitosan, dextran, hydroxyethyl cellulose, and soluble starch, with each polysaccharide that is present in the mixture being present in an amount of 0.05 to 0.5 wt. %, based on a total weight of the corrosion inhibitor composition, iii) silver nanoparticles, and iv) a pineapple leaves extract. A method of inhibiting corrosion of metal during acid cleaning/pickling whereby the metal is treated with an acidic treatment fluid containing an acid and the corrosion inhibitor composition.

FIELD OF THE INVENTION

The present invention relates to a corrosion inhibitor composition andmethods of inhibiting corrosion during acid cleaning/pickling.

DISCUSSION OF THE BACKGROUND

The “background” description provided herein is for the purpose ofgenerally presenting the context of the disclosure. Work of thepresently named inventors, to the extent it is described in thisbackground section, as well as aspects of the description which may nototherwise qualify as prior art at the time of filing, are neitherexpressly nor impliedly admitted as prior art against the presentinvention.

Titanium has become a choice metal for heat exchanger tubes inmulti-stage flash desalination plants owing to its good heat transferproperty and excellent erosion-corrosion properties. See I. N. Andijani,S. Ahmad, A. U. Malik. Corrosion behavior of titanium metal in presenceof inhibited sulfuric acid at 50° C. Presented at the InternationalDesalination Association World Congress on Desalination and Water Reuse,“The Value of Water in the 21st Century, San Diego, USA. 29 August,(1999); and I. N. Andijani, S. Ahmad, A. U. Malik, Corrosion behavior oftitanium metal in presence of inhibited sulfuric acid at 50° C.,Desalination 129 (2000) 45-51, each incorporated herein by reference intheir entirety. Normally, a multi-stage flash (MSF) desalination processinvolves the heating of seawater in a brine heater at the temperaturerange of 40-70° C. One of the challenges often encountered duringdesalination operations is excessive scale formation, mainly calciumcarbonate (CaCO₃) and magnesium hydroxide (Mg(OH)₂), and build-up insidethe metallic tubes. This usually leads to MSF desalination systemblockage. As a maintenance strategy, acid solutions (most commonly HClor H₂SO₄ in the concentration range of 1-5%) are used as a descalant toclean the tubes. However, descaling processes using corrosive acidsolutions are known to cause severe corrosion to titanium tubes. Toguard against the corrosion of the metallic structures, corrosioninhibitors are added to the acid solution to help prevent corrosion. SeeF. B. Mainier, L. P. C. Monteiro, S. S. M. Tavares, F. R. Leta, J. M.Pardal, Evaluation of titanium in hydrochloric acid solutions containingcorrosion inhibitors, IOSR Journal of Mechanical and Civil Engineering10(1) (2013) 66-69; and M. A. Deyab, Corrosion inhibition of heatexchanger tubing material (titanium) in MSF desalination plants in acidcleaning solution using aromatic nitro compounds, Desalination 439(2018) 73-79, each incorporated herein by reference in their entirety).Several organic and inorganic corrosion inhibitors for titanium havebeen reported.

For instance, Andijani et al. has reported CP-20, aβ-ethylphenylketocyclohexyl amino hydrochloride corrosion inhibitor. SeeI. N. Andijani, S. Ahmad, A. U. Malik, Corrosion behavior of titaniummetal in presence of inhibited sulfuric acid at 50° C., Desalination 129(2000) 45-51, incorporated herein by reference in its entirety. Mainieret al. evaluated the corrosion inhibition efficacy of thiocarbamide,phenylamine, and β-naphthol for titanium in solutions of hydrochloricacid (10% by mass) at 50 and 70° C. It was found that these compoundsexerted inhibition efficiency in the range 50 to 80%. See F. B. Mainier,L. P. C. Monteiro, S. S. M. Tavares, F. R. Leta, J. M. Pardal,Evaluation of titanium in hydrochloric acid solutions containingcorrosion inhibitors, IOSR Journal of Mechanical and Civil Engineering10(1) (2013) 66-69, incorporated herein by reference in its entirety.Aromatic nitro compounds have also been reported as effective corrosioninhibitors for titanium in acid cleaning solutions. See M. A. Deyab,Corrosion inhibition of heat exchanger tubing material (titanium) in MSFdesalination plants in acid cleaning solution using aromatic nitrocompounds, Desalination 439 (2018) 73-79, each incorporated herein byreference in their entirety. In the category of inorganic compounds,iodates, metavanadates, and molybdates have been found to effectivelyinduce the surface passivation of titanium and its alloys in HCl andH₂SO₄ solutions. See A. S. Mogoda, Y. H. Ahmad, W. A. Badawy. Corrosioninhibition of Ti-6Al-4V alloy in sulfuric and hydrochloric acidsolutions using inorganic passivators, Materials and Corrosion 55(6)(2004) 449-456, incorporated herein by reference in its entirety.Aromatic nitro compounds; hydroxylamine or its derivatives; compositionsof n-iodobensal-2-amino-5-nitrophenol,5-bromine-3-fluorine-butyl-6-methyluracil, and urotropin; andformulations of polyaspartic acid and ammonium molybdate at a mass ratioof 10:12 have also been described. See U.S. Pat. Nos. 2,962,356A,7,012,051B2, RU 2,261,292C2, and CN102330092A, each incorporated byreference in its entirety. However, these compounds/formulations mayachieve only moderate effectiveness at preventing corrosion, may beexpensive to make, and may be toxic to humans and the naturalenvironment.

In view of the forgoing, there is a need for effective, low cost, andenvironmentally friendly corrosion inhibitors that can be used forpreventing corrosion of metal during acid cleaning/pickling operations.

SUMMARY OF THE INVENTION

Accordingly, it is one object of the present invention to providecorrosion inhibitor compositions made primarily from natural polymersand plant extracts.

It is another object of the present invention to provide methods ofinhibiting corrosion of metal(s) during acid cleaning/picklingoperations by employing acidic treatment fluids containing an acid andthe corrosion inhibitor compositions for the dual purpose of removingdeposits such as scale from the metal while simultaneously protectingagainst corrosion.

Thus, the present invention provides:

A corrosion inhibitor composition which includes i) a base fluidcontaining water and an alcohol, ii) a mixture of at least threepolysaccharides selected from the group consisting of carboxymethylcellulose, gum arabic, pectin, a salt of alginic acid, chitosan,dextran, hydroxyethyl cellulose, and soluble starch, with eachpolysaccharide that is present in the mixture being present in an amountof 0.05 to 0.5 wt. %, based on a total weight of the corrosion inhibitorcomposition, iii) silver nanoparticles, and iv) a pineapple leavesextract.

In some embodiments, the alcohol is a monoalcohol.

In some embodiments, the alcohol is isopropanol.

In some embodiments, a ratio of water to the alcohol by volume is 2:1 to1:2.

In some embodiments, three polysaccharides are present in the mixture.

In some embodiments, each of the three polysaccharides is present in anamount of 30 to 40 wt. %, based on a total weight of the mixture.

In some embodiments, the mixture consists of carboxymethyl cellulose,gum arabic, and pectin.

In some embodiments, the silver nanoparticles are present in an amountof 0.005 to 0.1 wt. % based on a total weight of the corrosion inhibitorcomposition.

In some embodiments, the silver nanoparticles are in the form ofspherical nanoparticles having an average diameter of 30 to 100 nm.

In some embodiments, the pineapple leaves extract is an ethanolicpineapple leaves extract.

In some embodiments, the ethanolic pineapple leaves extract has a totalphenolic content of 15 to 50 mg per 100 mL of the pineapple leavesextract, as determined with high-performance liquid chromatography.

In some embodiments, the pineapple leaves extract is present in anamount of 0.01 to 0.1 wt. %, based on a total weight of the corrosioninhibitor composition.

A method of inhibiting corrosion of metal during acid cleaning/pickling,whereby the method involves treating the metal with an acidic treatmentfluid containing 1 to 5 wt. % of an acid, based on a total weight of theacidic treatment fluid, and 0.1 to 5 vol. % of the corrosion inhibitorcomposition, based on a total volume of the acidic treatment fluid.

In some embodiments, the corrosion inhibitor composition is present inthe acidic treatment fluid in an amount of 0.3 to 1 vol. %, based on atotal volume of the acidic treatment fluid.

In some embodiments, the acidic treatment fluid is acidified seawater,and the acid is hydrochloric acid.

In some embodiments, the metal is titanium.

In some embodiments, the metal is treated with the acidic treatmentfluid at a temperature of 40 to 70° C.

In some embodiments, the metal is treated with the acidic treatmentfluid under static conditions.

In some embodiments, the metal is treated with the acidic treatmentfluid under hydrodynamic conditions, whereby the metal is contacted withthe acidic treatment fluid at a flow rate of 0.5 to 5 m/s.

In some embodiments, the metal is present in a heat exchanger tube in adesalination plant, and the treating is performed to remove a buildup ofscale on the heat exchanger tube.

BRIEF DESCRIPTION OF THE DRAWINGS

The foregoing paragraphs have been provided by way of generalintroduction, and are not intended to limit the scope of the followingclaims. A more complete appreciation of the invention and many of theattendant advantages thereof will be readily obtained as the samebecomes better understood by reference to the following detaileddescription when considered in connection with the accompanyingdrawings, wherein:

FIG. 1 illustrates the structures of some of the possiblepolysaccharides in the corrosion inhibitor composition;

FIG. 2 is a picture of the corrosion inhibitor composition, alsoreferred to as “formulation” or “SOLOREN B”;

FIG. 3 is a bar graph showing the corrosion rate of Ti-Grade 2 inacidified seawater without and with 0.3 vol. % additives at differentimmersion durations at 40° C.;

FIG. 4 is a bar graph showing the corrosion rate of Ti-Grade 2 inacidified seawater without and with 0.4 vol. % additives at differentimmersion durations at 40° C.;

FIG. 5 is a bar chart showing the effectiveness of the formulation up to168 h at a concentration of 0.4 vol. %; FIG. 6 is a bar graph showingthe effectiveness of the formulation at 40 and 70° C. at a concentrationof 0.4 vol. %;

FIG. 7 illustrates the linear polarization resistance results showingthe variation of the corrosion rate of Ti-Grade 2 in acidified seawaterwithout and with additives at 40° C. at a concentration of 0.4 vol. %;and

FIG. 8 illustrates the linear polarization resistance results showingthe variation of the corrosion rate of Ti-Grade 2 in acidified seawaterwithout and containing 1% vol./vol. SOLOREN B at 40° C. underhydrodynamic conditions.

DETAILED DESCRIPTION OF THE INVENTION

In the following description, it is understood that other embodimentsmay be utilized and structural and operational changes may be madewithout departure from the scope of the present embodiments disclosedherein.

Definitions

As used herein, the term “fatty” describes a compound with a long-chain(linear) hydrophobic portion made up of hydrogen and anywhere from 6 to26, 8 to 24, 10 to 22, 12 to 20, 14 to 18 carbon atoms, which may befully saturated or partially unsaturated, and optionally attached to apolar functional group such as a hydroxyl group, an amine group, or acarboxyl group (e.g., carboxylic acid). Fatty alcohols, fatty amines,fatty acids, fatty esters, and fatty amides are examples of materialswhich contain a fatty portion, and are thus considered “fatty” compoundsherein.

As used herein, “alkoxylated” or “alkoxylate” refers to compoundscontaining a (poly)ether group (i.e., (poly)oxyalkylene group) derivedfrom reaction with, oligomerization of, or polymerization of one or morealkylene oxides having 2 to 4 carbon atoms, and specifically includes(poly)oxyethylene (derived from ethylene oxide, EO), (poly)oxypropylene(derived from propylene oxide, PO). and (poly)oxybutylene (derived frombutylene oxide, BO), as well as mixtures thereof.

The phrase “substantially free”, unless otherwise specified, describes aparticular component being present in an amount of less than about 1 wt.%, preferably less than about 0.5 wt. %, more preferably less than about0.1 wt. %, even more preferably less than about 0.05 wt. %, yet evenmore preferably 0 wt. %, relative to a total weight of the compositionbeing discussed.

As used herein, the terms “optional” or “optionally” means that thesubsequently described event(s) can or cannot occur or the subsequentlydescribed component(s) may or may not be present (e.g., 0 wt. %).

The term “alkyl”, as used herein, unless otherwise specified, refers toa straight, branched, or cyclic, aliphatic fragment having 1 to 26carbon atoms, preferably 2 to 24, preferably 3 to 22, preferably 4 to20, preferably 5 to 18, preferably 6 to 16, preferably 7 to 14,preferably 8 to 12, preferably 9 to 10. Non-limiting examples include,but are not limited to, methyl, ethyl, propyl, isopropyl, butyl,isobutyl, t-butyl, pentyl, isopentyl, neopentyl, hexyl, isohexyl,3-methylpentyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, lauryl, myristyl,cetyl, stearyl, and the like, including guerbet-type alkyl groups (e.g.,2-methylpentyl, 2-ethylhexyl, 2-proylheptyl, 2-butyloctyl,2-pentylnonyl, 2-hexyldecyl, 2-heptylundecyl, 2-octyldodecyl,2-nonyltridecyl, 2-decyltetradecyl, and 2-undecylpentadecyl), andunsaturated alkenyl and alkynyl variants such as vinyl, allyl,1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl,2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl,4-hexenyl, 5-hexenyl, oleyl, linoleyl, and the like. Cycloalkyl is atype of cyclized alkyl group. Exemplary cycloalkyl groups include, butare not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,norbornyl, and adamantyl. The term “lower alkyl” is used herein todescribe alkyl groups having 1 to 5 carbon atoms (e.g., methyl, ethyl,n-propyl, etc.).

As used herein, unless otherwise specified, the term “aryl” refers to anaromatic group containing only carbon in the aromatic ring(s), such asphenyl, biphenyl, naphthyl, anthracenyl, and the like. The term“heteroarene” or “heteroaryl” refers to an arene compound or aryl groupwhere at least one carbon atom is replaced with a heteroatom (e.g.,nitrogen, oxygen, sulfur) and includes, but is not limited to, pyridine,pyrimidine, quinoline, isoquinoline, pyrazine, pyridazine, indole,pyrrole, oxazole, furan, benzofuran, thiophene, benzothiophene,isoxazole, pyrazole, triazole, tetrazole, indazole, purine, carbazole,imidazole, and benzimidazole.

As used herein, “alkanoyloxy” groups are alkanoyl groups that are boundto oxygen (—O—C(O)-alkyl), for example, acetyloxy, propionyloxy,butyryloxy, isobutyryloxy, pivaloyloxy, valeryloxy, hexanoyloxy,octanoyloxy, lauroyloxy, and stearoyloxy. “Alkoxycarbonyl” substituentsare alkoxy groups bound to C═O (e.g. —C(O)—Oalkyl), for example methylester, ethyl ester, and pivaloyl ester substitution where the carbonylfunctionality is bound to the rest of the compound.

As used herein, “optionally substituted” means that at least onehydrogen atom is replaced with a non-hydrogen group, provided thatnormal valencies are maintained and that the substitution results in astable compound. Such optional substituents may be selected from aryl,alkoxy, aryloxy, arylalkyloxy, alkanoyloxy, carboxy, alkoxycarbonyl,hydroxy, halo (e.g. chlorine, bromine, fluorine or iodine), amino (e.g.alkylamino, arylamino, arylalkylamino, alkanoylamino, either mono- ordisubstituted), oxo, amido (e.g. —CONH₂, —CONHalkyl, —CONHaryl,—CONHarylalkyl or cases where there are two substituents on onenitrogen), and the like.

As used herein, “inhibit” means prevent, retard, slow, hinder, reverse,remove, lessen, reduce an amount of, or delay an undesirable process oran undesirable composition, or combinations thereof.

As used herein the term “corrosion inhibitor” refers to a substance(s)or composition that inhibits the deterioration of a metal surface byoxidation or other chemical reaction.

Corrosive substances that can cause corrosion include water with highsalt contents, acidic inorganic compounds such as hydrochloric acid,hydrofluoric acid, carbon dioxide (CO₂) and/or hydrogen sulfide (H₂S),organic acids, and microorganisms. Preferred corrosion inhibitors of thepresent invention inhibit the destructive effect such substances have onvarious metal surfaces.

“Scale” is a mineral salt deposit or coating formed on the surface ofmetal, rock or other material. Scale is caused by a precipitation due toa chemical reaction with the surface, precipitation caused by chemicalreactions, a change in pressure or temperature, or a change in thecomposition of a solution. Exemplary scales include, but are not limitedto, calcium carbonate, magnesium hydroxide, calcium sulfate, bariumsulfate, strontium sulfate, iron sulfide, iron oxides, iron carbonate,the various silicates and phosphates and oxides, or any of a number ofcompounds insoluble or slightly soluble in water.

As used herein, the terms “scale inhibitor” or “antiscalant” refers to asubstance(s) that inhibits the accumulation or buildup of unwanted scale(including reverses, cleans, removes, or otherwise reduces/lessens anamount of scale already existing on a surface), for example thosesurfaces exposed to brine-containing solutions during desalinationprocesses.

Corrosion Inhibitor Composition

The present disclosure provides a corrosion inhibitor composition. Thecorrosion inhibitor composition of the present disclosure may beeffective for inhibiting corrosion of various metals caused by acidicfluids, in particular, the corrosion of titanium metals caused by acidicfluids used for the removal of scale from various process equipment,such as process equipment used in desalination operations where scalebuildup is particularly problematic, as is the case in heat exchangersand utility steam condensers in multi-stage flash desalination plants.

The corrosion inhibitor composition disclosed herein generallycomprises, consists essentially of, or consists of an aqueous alcoholbase fluid, a mixture of polysaccharides, preferably threepolysaccharides, silver nanoparticles that are preferably formed insitu, and a pineapple leaves extract.

Base Fluid

The base fluid typically accounts for the majority of the corrosioninhibitor composition, and is designed to aid solvation of the variousingredients as well as facilitate transfer of the corrosion inhibitorcomposition. In some embodiments, the corrosion inhibitor compositioncontains at least 90 wt. %, preferably at least 92 wt. %, preferably atleast 94 wt. %, preferably at least 96 wt. %, preferably at least 98 wt.%, preferably at least 99 wt. %, preferably at least 99.2 wt. %,preferably at least 99.4 wt. %, preferably at least 99.6 wt. %, based ona total weight of the corrosion inhibitor composition.

The base fluid may be an aqueous alcohol base fluid comprising,consisting essentially of, or consisting of water and an alcohol. Insome embodiments, a v/v ratio of water to the alcohol is from 3:1 to1:3, preferably 2.5:1 to 1:2.5, preferably 2:1 to 1:2, preferably 1.5:1to 1:1.5, preferably 1:1. In preferred embodiments, the base fluidconsists of water and the alcohol.

The water may be distilled water, tap water, well water, purified water,or fresh water obtained from natural sources such as lakes, streams,rivers, etc.

The alcohol may be a monoalcohol, a polyalcohol, or a combinationthereof. Exemplary monoalcohols include, but are not limited to,methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol,n-pentanol, n-hexanol, 3-methyl-3-buten-l-ol, 2-ethyl-1-hexanol,2-ethyl-1-butanol, 2-propylheptan-1-ol, and 2-butyl-1-octanol, includingmixtures thereof. Exemplary polyalcohols include, but are not limitedto, ethylene glycol, diethylene glycol, triethylene glycol,tetraethylene glycol, propylene glycol, dipropylene glycol,1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol,glycerol, pentaerythritol, manitol, and sorbitol, including mixturesthereof. In preferred embodiments, the alcohol is a monoalcohol,preferably one of methanol, ethanol, propanol, isopropanol, andisobutanol, preferably isopropanol.

Other organic solvents may also be included in the base fluid (inaddition to the alcohol described above), for example to aid solvationof the various ingredients of the corrosion inhibitor composition. Theother organic solvent(s) may be added in amounts of 1 to 20 vol. %,preferably 3 to 15 vol. %, preferably 5 to 10 vol. %, preferably 6 to 8vol. %, based on a total volume of the base fluid. The other organicsolvent may any solvent that is miscible with water, preferably a polaraprotic solvent. Acceptable other organic solvents include, but are notlimited to, formamide, dimethyl formamide, dimethyl acetamide, acetone,methyl ethyl ketone, ethylene glycol methyl ether, ethylene glycol ethylether, ethylene glycol propyl ether, and ethylene glycol butyl ether.

Mixture of Polysaccharides

The corrosion inhibitor compositions disclosed herein also include amixture of polysaccharides, preferably a mixture of at least threepolysaccharides, preferably a mixture of at least four polysaccharides,preferably a mixture of at least five polysaccharides. Thepolysaccharides may provide several benefits. Firstly, thepolysaccharides may contribute to the overall anti-corrosivity of thecorrosion inhibitor compositions as individual components, and inparticularly when used in combination of three or more where synergisticanti-corrosion effects are seen. Secondly, the polysaccharides mayfunction as dispersants for the silver nanoparticles, and thus may aidin preventing the formation of silver nanoparticle agglomerates.

The polysaccharides employed herein are preferably polysaccharidesobtained from natural sources or are semi-synthetic polysaccharides thatcan be easily derived from natural polysaccharides and produced easily,cheaply, and in large-scale. Examples of polysaccharides that may beincluded in the corrosion inhibitor compositions of the presentdisclosure include, but are not limited to, modified cellulose polymers(e.g., hydroxyethyl cellulose (HEC), hydroxypropylmethylcellulose(HPMC), methylcellulose (MC), and carboxymethyl cellulose (CMC)); gumarabic (acacia); pectin; a salt of alginic acid (e.g., sodium alginate,potassium alginate, ammonium alginate, and/or calcium alginate);chitosan; dextran; modified starch such as soluble starch (e.g., coldwater soluble starches) and cold-water swellable starch; xanthan gum;guar gum; carrageenan; locust bean gum; agar; tapioca; inulin; glycogen,and covalently modified alginates (e.g., propylene glycol alginates);and mixtures thereof.

In preferred embodiments, the mixture is made up of at least threepolysaccharides selected from the group consisting of carboxymethylcellulose, gum arabic, pectin, a salt of alginic acid (e.g., sodiumalginate), chitosan, dextran, hydroxyethyl cellulose, and solublestarch. Each of these polysaccharides may be optionally included in themixture and will be briefly described below.

-   -   Carboxymethyl cellulose (CMC) is a cellulose derivative with        carboxymethyl groups (—CH₂—COOH) bound to some of the hydroxyl        groups of the glucopyranose monomers that make up the cellulose        backbone (comprised of β(1→4) linked D-glucose units).        Carboxymethyl cellulose may be in the form of a free acid or a        carboxylate salt (e.g., sodium salt). The carboxymethyl        cellulose employed in the present disclosure may have a degree        of substitution, in terms of carboxymethyl groups per        anhydroglucose unit in the cellulose backbone, of 0.6 to 1.4,        preferably 0.7 to 1.3, preferably 0.8 to 1.2, preferably 0.9 to        1.1, preferably 1.0. In preferred embodiments, the carboxymethyl        cellulose employed herein may have a weight average molecular        weight of 80,000 g/mol to 800,000, preferably 90,000 g/mol to        700,000, preferably 100,000 g/mol to 600,000, preferably 120,000        g/mol to 500,000, preferably 140,000 g/mol to 400,000,        preferably 160,000 g/mol to 300,000, preferably 180,000 g/mol to        250,000, preferably 200,000 g/mol to 220,000 g/mol. In preferred        embodiments, the carboxymethyl cellulose is sodium carboxymethyl        cellulose having a weight average molecular weight of 240,000 to        260,000 g/mol and a degree of substitution of 0.85 to 0.95;    -   Gum Arabic (also known as acacia gum) is a polydisperse natural        gum collected from acacia species, predominantly Acacia senegal        and Vachellia (Acacia) seyal, which is a complex mixture of        glycoproteins and polysaccharides predominantly made from        arabinose and galactose monomers. In some embodiments, the gum        arabic employed in the present disclosure is a branched polymer        comprising galactose, rhamnose, arabinose, and glucuronic acid        as a mixed salt of calcium, magnesium, and potassium. In some        embodiments, the gum arabic has a weight average molecular        weight of 160,000 g/mol to 300,000, preferably 180,000 g/mol to        290,000, preferably 200,000 g/mol to 280,000, preferably 220,000        g/mol to 270,000, preferably 240,000 g/mol to 260,000,        preferably 250,000 g/mol. The gum arabic used herein may be a        spray dried form, for example a spray dried gum arabic with a        weight loss of less than 10 wt. %, preferably less than 5 wt. %,        preferably less than 3 wt. % on drying. The gum arabic may have        a bulk density of 380 to 420 kg/m³, preferably 390 to 410 kg/m³,        preferably 400 kg/m³;    -   Pectin is a structural heteropolysaccharide, rich in        galacturonic acid, contained in the primary cell walls of        terrestrial plants. It is produced commercially as a white to        light brown powder, mainly extracted from citrus fruits. Several        distinct polysaccharides have been identified and characterized        within the pectic group. Homogalacturonans are linear chains of        α-(1-4)-linked D-galacturonic acid. Substituted galacturonans        are characterized by the presence of saccharide appendant        residues (such as D-xylose or D-apiose in the respective cases        of xylogalacturonan and apiogalacturonan) branching from a        backbone of D-galacturonic acid residues. Rhamnogalacturonan I        pectins (RG-I) contain a backbone of the repeating disaccharide        4)-α-D-galacturonic acid-(1,2)-α-L-rhamnose-(1. From many of the        rhamnose residues, sidechains of various neutral sugars branch        off. The neutral sugars are mainly D-galactose, L-arabinose and        D-xylose, with the types and proportions of neutral sugars        varying with the origin of pectin. Another structural type of        pectin is rhamnogalacturonan II (RG-II), which is a complex,        highly branched polysaccharide with a backbone made exclusively        of D-galacturonic acid units. In nature, around 80 percent of        carboxyl groups of galacturonic acid are esterified with        methanol. This proportion is decreased to a varying degree        during pectin extraction. The ratio of esterified to        non-esterified galacturonic acid is one factor that determines        the properties of pectin. Pectins may be classified as        high-ester pectins (more than half of all the galacturonic acid        is esterified) or low-ester pectins (less than half of all the        galacturonic acid is esterified). In some embodiments, the        pectin utilized herein is a rhamnogalacturonan II (RG-II)        pectin. In preferred embodiments, the pectin utilized herein is        a rhamnogalacturonan I (RG-I) pectin. The pectin herein may be        obtained from citrus peel or apple peel. In some embodiments,        the pectin is a high ester pectin, preferably a pectin having 50        to 95%, preferably 52 to 94%, preferably 55 to 92%, preferably        60 to 90%, preferably 64 to 88%, preferably 68 to 86%,        preferably 70 to 84%, preferably 72 to 82%, preferably 74 to        80%, preferably 76 to 78% of a total galacturonic acid content        in the form of a methyl ester. In some embodiments, the pectin        is a low ester pectin, preferably a pectin having less than 45%,        preferably less than 40%, preferably less than 35%, preferably        less than 30%, preferably less than 25%, preferably less than        20%, preferably less than 15%, preferably less than 10%,        preferably less than 5% of a total galacturonic acid content in        the form of a methyl ester. The non-esterified galacturonic acid        units of the pectin used herein can be either free acids        (carboxylic acid groups) or salts with sodium, potassium, and/or        calcium. The molecular weight of pectin also varies depending on        the origin of the pectin and the extraction conditions. In some        embodiments, the pectin has a weight average molecular weight of        50,000 to 150,000 g/mol, preferably 60,000 to 140,000 g/mol,        preferably 70,000 to 130,000 g/mol, preferably 80,000 to 120,000        g/mol, preferably 90,000 to 110,000 g/mol, preferably 100,000        g/mol;    -   Alginic acid is a polyuronic acid generally believed to consist        of two uronic acids; mannuronic acid and guluronic acid, the        proportions of which vary depending on factors such as, for        example, seaweed species, plant age, and seasonal variation.        Specifically, alginic acid is a linear copolymer with        homopolymeric blocks of (1-4)-linked β-D-mannuronate (M) and its        C-5 epimer α-L-guluronate (G) residues, respectively, covalently        linked together in different sequences or blocks. Alginic acid        in the form of mixed water insoluble salts, in which the        principal cation is calcium, is present in seaweeds of the Class        Phaeophyceae, typical examples of which include, but are not        limited to, Fucus vesiculosus, F. spiralis, Ascophyllum nodosum,        Macrocystis pyrifera, Alaria esculenta, Laminaria        longicruris, L. digitata, L. saccharina, and L. cloustoni.        Alginic acid salts such as sodium alginate, potassium alginate,        ammonium alginate, calcium alginate, as well as mixed salt forms        may be used herein. Methods for the recovery of water insoluble        alginic acid and its water soluble salts, particularly sodium        alginate, are well known, see for example U.S. Pat. No.        3,948,881A and references cited therein, incorporated herein by        reference in its entirety. The structure, molecular weight, and        thus the properties (viscosity) of the salt of alginic acid may        depend on several factors, including but not limited to the        seaweed origin, the extraction method, and the final salt form.        In preferred embodiments, when a salt of alginic acid is        employed in the corrosion inhibitor composition, sodium alginate        is preferred. Preferably, the sodium alginate is extracted from        brown algae, such as Laminaria hyperborea, Laminaria digitata,        Laminaria japonica, Ascophyllum nodosum, and Macrocystis        pyrifera. In some embodiments, the sodium alginate is a low        viscosity type, having a viscosity less than 150 cP, preferably        less than 100 cP, preferably less than 80 cP, preferably less        than 60 cP, preferably less than 40 cP, preferably less than 20        cP, measured as a 1 wt. % solution in water. In some        embodiments, the sodium alginate is a medium viscosity type,        having a viscosity from 150 to 400 cP, preferably 175 to 375 cP,        preferably 200 to 350 cP, preferably 225 to 300 cP, preferably        250 to 275 cP, measured as a 1 wt. % solution in water. In some        embodiments, the sodium alginate is a high viscosity type,        having a viscosity above 400 cP and up to 1,000 cP, preferably        from 450 to 950 cP, preferably 500 to 900 cP, preferably 550 to        850 cP, preferably 600 to 800 cP, preferably 650 to 750 cP,        preferably 700 cP. The weight average molecular weight of the        sodium alginate may range from 32,000 to 400,000 g/mol,        preferably 40,000 to 360,000 g/mol, preferably 60,000 to 320,000        g/mol, preferably 80,000 to 300,000 g/mol, preferably 100,000 to        260,000 g/mol, preferably 120,000 to 240,000 g/mol, preferably        140,000 to 200,000 g/mol. The sodium alginate salt may be in the        form of crude particulates (for example having an average        particle size of >200 μm and up to 3 mm), medium particulates        (for example having an average particle size of 100 to 200 μm,        preferably 120 to 180 μm, preferably 140 to 160 μm), or fine        particulates (for example having an average particle size of 30        to 80 μm, preferably 40 to 70 μm, preferably 50 to 60 μm);    -   Chitosan, the deacylated form of chitin, is a linear        polysaccharide composed of randomly distributed β-(1→4)-linked        D-glucosamine (deacetylated unit) and N-acetyl-D-glucosamine        (acetylated unit). Chitosan may be made by treating the chitin        shells of crab, shrimp, squid, and other crustaceans or the cell        walls of fungi either by enzymatic preparations or chemical        hydrolysis using any procedure known by those of ordinary skill        in the art, for example as disclosed in U.S. Pat. Nos.        7,544,785B2, 4,195,175A, and US20040215005A1—each incorporated        herein by reference in its entirety. Chitosan materials derived        from various sources, and having various chemical/physical        properties (e.g., degree of deacetylation (DD), molecular weight        distribution, viscosity, etc.) are generally effective when        employed in the corrosion inhibitor compositions herein. The        chitosan employed herein may be derived from chitin of animal        sources, preferably shrimp shells. Alternatively, the chitosan        may be derived from chitin of non-animal sources, preferably        from fungal fermentation. The degree of deacetylation reflects        the balance between the two kinds of monomeric residues in        chitosan, and is defined as the molar fraction of deacylated        units present, i.e., the average number of deacylated units        (β-(1→4)-linked D-glucosamine) divided by the sum of the average        number of both deacylated and acylated units, expressed as a        percentage (Balázs, N., Sipos, P., Limitations of        pH-potentiometric titration for the determination of the degree        of deacetylation of chitosan, Carbohydrate Research, 342 (1),        124-130, 2007—incorporated herein by reference in its entirety).        In some embodiments, the chitosan has a degree of deacetylation        (DD) of at least 40%, preferably at least 50%, preferably at        least 60%, preferably at least 70%, preferably at least 72%,        preferably at least 74%, preferably at least 75%, preferably at        least 78%, preferably at least 80%, preferably at least 82%,        preferably at least 85%, and up to 99%, preferably up to 98%,        preferably up to 96%, preferably up to 95%, preferably up to        93%, preferably up to 90%, preferably up to 88%. The DD may be        determined by any method known by those of ordinary skill, for        example, by NMR, IR, acid-base titrimetry, potentiometer        titrimetry, or first derivative UV spectroscopy (Khan, T. A. et        al. Reporting the degree of deacetylation values of chitosan:        the influence of analytical methods, J Pharm. Pharmaceut. Sci.        2002, 5(3):205-212; Jiang, T. D. Chitosan; Chemical industry        press: Beijing, China, 2001; pp. 91, 100, 108; Broussignac, P.        Un polymere natural pecu cannu dans 1′ industrie e chitosane.        Chim. Ind.-Genie Chim. 1970, 99, 1241-1247; Muzzarelli, R. A.        A.; Rocchetti, R.

Determination of the degree of acetylation of chitosans by firstderivative ultraviolet spectrophotometry. Carbohydr. Polym. 1985, 5,461-472; Yuan, Y. et al. Materials, 2011, 4, 1399-1416—each incorporatedherein by reference in its entirety). In some embodiments, the chitosanhas a weight average molecular weight of 440 to 375,000 g/mol,preferably 500 to 350,000 g/mol, preferably 800 to 300,000 g/mol,preferably 1,000 to 250,000 g/mol, preferably 5,000 to 200,000 g/mol,preferably 10,000 to 150,000 g/mol, preferably 20,000 to 100,000 g/mol,as determined for example by size exclusion chromatography. In someembodiments, the chitosan has a viscosity (as a 1 wt. % solution in 1wt. % acetic acid) of 20 to 3,000 cP, preferably 40 to 2,500 cP,preferably 60 to 2,000 cP, preferably 80 to 1,500 cP, preferably 100 to1,000 cP, preferably 120 to 800 cP, preferably 140 to 600 cP, preferably160 to 400 cP, preferably 180 to 300 cP, preferably 200 to 250 cP asdetermined by a viscometer (e.g., Brookfield viscometer made by AMETEKBrookfield) at 25° C.;

-   -   Dextran is a complex branched glucan (polysaccharide derived        from the condensation of glucose), with a polymer main chain        consisting of α-1,6 glycosidic linkages between glucose        monomers, with branches from α-1,3 linkages (approximately 95%        alpha-D-(1-6) linkages with the remaining α-(1-3) linkages        accounting for the branching of dextran). This characteristic        branching distinguishes a dextran from a dextrin, which is a        straight chain glucose polymer tethered by α-1,4 or α-1,6        linkages. Dextran may be produced from sucrose by certain lactic        acid bacteria of the family lactobacillus, such as Leuconostoc        mesenteroides and Streptococcus mutans. The structure of dextran        produced depends not only on the family and species of the        bacterium but on the strain. Dextrans are typically separated by        fractional precipitation from protein-free extracts using        ethanol, as is known by those of ordinary skill in the art. In        some embodiments, dextrans employed herein are derived from        Leuconostoc mesenteroides, strain B 512. Dextrans can be        produced in a wide range of molecular weights by limited        hydrolysis and fractionation (e.g., size exclusion        chromatography). In some embodiments, the dextran may have a        weight average molecular weight of 1 to 2,000 kDa, preferably 2        to 1,500 kDa, preferably 3 to 1,000 kDa, preferably 4 to 800        kDa, preferably 5 to 600 kDa, preferably 8 to 400 kDa,        preferably 10 to 200 kDa, preferably 15 to 100 kDa, preferably        20 to 50 kDa. In some embodiments, the dextran has a        polydispersity (M_(w)/M_(n)) of 1.2 to 1.8, preferably 1.25 to        1.65, preferably 1.3 to 1.6, preferably 1.35 to 1.55, preferably        1.4 to 1.5, preferably 1.45;    -   Hydroxyethyl cellulose is a cellulose derivative with        hydroxyethyl groups (—CH₂CH₂OH) bound to some of the hydroxyl        groups of the glucopyranose monomers, similar to carboxymethyl        derivatives of cellulose described above, typically made by        hydroxyethylating the unsubstituted anhydroglucose units of        cellulose with ethylene oxide. The hydroxyethyl cellulose        employed in the present disclosure may have a molar substitution        (M.S.), in terms of mols of hydroxyethyl groups per mol of        cellulose, of 1.0 to 2.5, preferably 1.2 to 2.3, preferably 1.4        to 2.1, preferably 1.6 to 2.0, preferably 1.8 to 1.9. In        preferred embodiments, the carboxymethyl cellulose employed        herein may have a weight average molecular weight of 80,000        g/mol to 800,000, preferably 90,000 g/mol to 700,000, preferably        100,000 g/mol to 600,000, preferably 120,000 g/mol to 500,000,        preferably 140,000 g/mol to 400,000, preferably 160,000 g/mol to        300,000, preferably 180,000 g/mol to 250,000, preferably 200,000        g/mol to 220,000 g/mol;    -   Soluble starches are starches that have been modified in some        way to improve the functional solubility of the starch material        (and in some cases other properties of the starch material such        as the ability to withstand heat, shear, and acidic pH). The        soluble starch employed herein may be modified via chemical        and/or physical processes. Soluble starches may be chemically        modified by oxidation, cross-linking, stabilization, and        depolymerization. Soluble starches may be physically modified,        for example, by pregalatinization. The soluble starch may be a        stabilized starch (e.g., hydroxypropyl starches, starch        acetates, starch octenylsuccinates, monostarch phosphate, etc.),        a cross-linked starch (e.g., distarch phosphate, distarch        adipate, etc.), a cross-linked and stabilized starch (e.g.,        hydroxypropylated distarch phosphate, phosphorylated distarch        phosphate, acetylated distarch phosphate, acetylated distarch        adipate, etc.), an oxidized starch (e.g., hypochlorite-oxidized        starch, etc.), a thinned (depolymerized) starch such as those        starches depolymerized by acid or base treatment (e.g.,        alcoholic-alkaline treated starch), and a physically processed        starch such as pre-gelatinized starch. Any starch may be        modified to produce the soluble starches of the present        disclosure, for example starch derived from corn, potato,        tapioca, wheat, rice, etc. Preferably the soluble starch is        derived from common corn, waxy maize, or tapioca. Specific        examples of soluble starches may include, but is not limited to,        COLD WATER SOLUBLE STARCH VS-CS, PREGELATINIZED STARCH-MAIZE        (VS-PMS), -POTATO (VS-PPS), each available from Visco Starch,        INSTANT TEXTRA, available from Ingredion), and soluble starch        (S9765) available from Sigma-Aldrich.

Each polysaccharide that is present in the mixture may be present in anamount of 0.05 to 0.5 wt. %, preferably 0.06 to 0.4 wt. %, preferably0.07 to 0.35 wt. %, preferably 0.08 to 0.3 wt. %, preferably 0.09 to0.25 wt. %, preferably 0.1 to 0.2 wt. %, preferably 0.105 to 0.15 wt. %,based on a total weight of the corrosion inhibitor composition.

In some embodiments, the mixture consists of three polysaccharides,wherein each of the three polysaccharides is present in an amount of 30to 40 wt. %, preferably 31 to 38 wt. %, preferably 32 to 36 wt. %,preferably 33 wt. %, based on a total weight of the mixture. Inpreferred embodiments, the three polysaccharides are present inequivalent amounts (1:1:1 weight ratio or where each of the threepolysaccharides is present in the mixture in an amount of 33 wt. %,based on a total weight of the mixture).

In some embodiments, the mixture contains (at least) carboxymethylcellulose, gum arabic, and pectin. Preferably, the mixture containscarboxymethyl cellulose, gum arabic, and pectin, and is substantiallyfree of all other polysaccharides (e.g., carrageenan, chitosan, alginicacid and salts, etc.). In preferred embodiments, the mixture consists ofcarboxymethyl cellulose, gum arabic, and pectin.

Silver Nanoparticles

The corrosion inhibitor composition also includes silver nanoparticles,preferably silver nanoparticles which are formed through the reductionof a silver salt in situ. The silver nanoparticles may be in the form ofvarious shapes such as spheres, spheroids, ellipsoids or polygons,preferably in the form of spheres.

In some embodiments, the silver nanoparticles have an average diameterof 30 to 100 nm, preferably 40 to 90 nm, preferably 50 to 80 nm,preferably 60 to 70 nm. For particles with a polygonal shape, the term“diameter”, as used herein, refers to the greatest possible distancemeasured from a vertex of a polygon through the center of the face tothe vertex on the opposite side. For spheres, spheroids, ellipsoids andirregular-shaped particles, “diameter” refers to the greatest possibledistance measured from one point on the particle through the center ofthe particle to a point directly across from it. The silvernanoparticles may be monodisperse. “Dispersity” is a measure of thehomogeneity/heterogeneity of sizes of particles in a mixture. Thecoefficient of variation (CV), also known as relative standard deviation(RSD) is a standardized measure of dispersion of a probabilitydistribution. It is expressed as a percentage and may be defined as theratio of the standard deviation (σ) to the mean (μ, or its absolutevalue |μ|), and it may be used to show the extent of variability inrelation to the mean of a population. The silver nanoparticles may havea narrow size dispersion, i.e., are monodisperse, with a coefficient ofvariation of less than 30%, preferably less than 25%, preferably lessthan 20%, preferably less than 15%, preferably less than 12%, preferablyless than 10%, preferably less than 8%, preferably less than 5%,preferably less than 3%, with the coefficient of variation being definedin this context as the ratio of the standard deviation to the meandiameter of the silver nanoparticles, as calculated using transmissionelectron microscopy for example. Alternatively, the silver nanoparticlesmay be polydisperse, i.e., have a wide size distribution, with acoefficient of variation of at least 30%, preferably at least 35%,preferably at least 40%, preferably at least 45%, preferably at least50%, preferably at least 55%, preferably at least 60%.

Various amounts of silver nanoparticles may be used in the corrosioninhibitor compositions for effective corrosion inhibition, however,typical amounts may range from 0.005 to 0.1 wt. %, preferably 0.006 to0.09 wt. %, preferably 0.008 to 0.08 wt. %, preferably 0.01 to 0.07 wt.%, preferably 0.012 to 0.06 wt. %, preferably 0.014 to 0.05 wt. %,preferably 0.016 to 0.04 wt. %, preferably 0.018 to 0.03 wt. %,preferably 0.02 to 0.025 wt. %, preferably 0.021 to 0.022 wt. %, basedon a total weight of the corrosion inhibitor composition.

As will be discussed hereinafter, the silver nanoparticles arepreferably formed in situ through reduction of a silver salt by apineapple leaves extract. After being reduced, the silver nanoparticlesmay also be stabilized by the pineapple leaves extract and/or one ormore of the polysaccharides present in the mixture, and are thuspreferably homogeneously dispersed throughout the corrosion inhibitorcomposition as separated particles, i.e., the silver nanoparticlespreferably do not agglomerate/form silver agglomerates as they arebeing/once they are reduced. Preferably, an average distance between thesilver nanoparticles, measured as the distance between an outer surfaceof a first nanoparticle to an outer surface of a second nanoparticlelocated closest to the first nanoparticle, ranges from 10 to 200 nm,preferably 20 to 150 nm, preferably 30 to 100 nm, preferably 40 to 80nm.

Without being bound by theory, it is believed that the silvernanoparticles, once reduced, are incorporated/encapsulated into thebiopolymer matrix formed from the mixture of polysaccharides. Thepineapple leaves extract, as discussed below, is believed to act as thereducing agent for the in situ reduction of the silver salts, and alsoas a capping agent/dispersant to prevent agglomeration of the newlysilver nanoparticles.

In preferred embodiments, all of the silver salt is reduced to formsilver nanoparticles, and thus the corrosion inhibitor composition ispreferably substantially free of silver salts, preferably substantiallyfree of silver(I) salts (i.e., Ag⁺ ions).

Pineapple Leaves Extract

The corrosion inhibitor compositions also include a pineapple extract.It has been found that the pineapple extract provides the corrosioninhibitor compositions with particularly beneficial anticorrosionproperties. The pineapple extract may not only act as a reducing agentfor converting silver salts into the silver nanoparticles, but it isbelieved that the pineapple extract may also serve as acapping/dispersing agent for the silver nanoparticles, preventing theiragglomeration, thereby enhancing the anticorrosion effects of thecorrosion inhibitor compositions.

Ananas comosus (L.) Merr. (family Bromeliaceae), commonly known aspineapple, has long been one of the most popular of tropical andsubtropical fruits. It is grown extensively in Hawaii, Philippines,Caribbean area, Malaysia, Taiwan, Thailand, Australia, Mexico, Kenya,South Africa, Hainan province of China among many other locations.Besides agricultural utilities, such as being a fruit with nutritionalvalue, many parts of the pineapple have been harvested for various uses,such as the pineapple fruit, residual pulp, stem, peel, and leaves. Eachof these parts contain a different chemical constitution that can beused for varying applications and benefits. For example, the pineapplestem and fruit are commonly of interest because they contain arelatively high content of bromelain, a protein digesting enzymepossessing anti-inflammatory properties. Pineapple leaves are typicallyharvested for their fibers (pineapple leaf fibers or PALF), which haveexcellent mechanical properties and can be in various textiles and asreinforcing fibers in various composites. Pineapple peel has been usedfor the alkali extraction of ferulic acid, a phenolic antioxidant foundin the peel.

For making an extract, in addition to the part of the pineappleharvested, the extraction procedure, particularly the extractionsolvent, dictates the chemical make-up of the extract, as is wellunderstood in the art (see for example Upadhyay, A. et al, “Utilizationof Pineapple Waste: A Review” Journal of Food Science and TechnologyNepal, 6, 10-18; Kaushik, J. et al. “Phytochemical Screening,Anti-oxidant and Anti-Microbial Activity of Polyphenolic FlavonoidsIsolated from fruit of Ananas comosus in various solvents” InternationalJournal of Scientific and Research Publications, 2018, 8(2), 31-55, eachincorporated herein by reference in its entirety.

The pineapple extract used in the corrosion inhibitor composition ispreferably a pineapple leaves extract. Pineapple leaves typicallycontain carbohydrates, alkaloids, saponins, sterols/terpenes,flavanoids, tannins, phenolic compounds, proteins, amino acids,phytosterol, and glycosides. The pineapple leaves extract may beemployed in varying quantities with beneficial effect, though thepineapple leaves extract is typically employed in an amount of 0.005 to0.5 wt. %, preferably 0.006 to 0.3 wt. %, preferably 0.008 to 0.2 wt. %,preferably 0.01 to 0.1 wt. %, preferably 0.02 to 0.09 wt. %, preferably0.03 to 0.08 wt. %, preferably 0.04 to 0.06 wt. %, preferably 0.05 wt.%, preferably based on a total weight of the corrosion inhibitorcomposition.

The pineapple extract is preferably obtained from extraction ofpineapple leaves with an ethanolic solvent, for example 80 to 100 wt. %ethanol, preferably 85 to 95 wt. % ethanol, preferably 90 wt. % ethanol(the balance being water).

In one example, the ethanolic pineapple leaves extract may be obtainedby drying the Ananas comosus leaves for example at room temperature orunder sun-drying conditions, and the dried leaves may then bepowdered/ground, for example with an electrical grinder. The powderedleaves may be optionally delipidated with a hydrocarbon solvent (e.g.,petroleum ether, pentane, hexane, heptane, etc.) at 20 to 80° C.,preferably 40 to 60° C. prior to extraction. Extraction may beperformed, for example, using a soxhlet extractor or similar extractionapparatus with an ethanolic solvent described above under conditions ofreflux, preferably with 95 wt. % ethanol. Alternatively, extraction maybe performed using cold extraction techniques, for example by soaking orstirring the powdered leaves in the ethanolic solvent for an extendedperiod, such as for 24 to 96 hours, preferably 48 to 72 hours. In eithercase, the extraction supernatant may be separated from any bulk solidmaterial, for example by filtration, and the ethanolic solvent may thenbe evaporated from the extract, for example using a rotary evaporatorunder reduced pressure and optional elevated temperature (e.g., 40 to50° C.) to provide the ethanolic pineapple leaves extract as theremaining solid residue. When ethanolic solvents are used containingrelatively high amounts of water, such as when 80 wt. % ethanolsolutions are used as the extraction solvent, the method may optionallyinvolve further drying operations, for example using heat baths, ovens,or vacuum drying, to remove excess water. Typical yields of theethanolic pineapple leaves extract may range from 15 to 30%, preferably25 to 28%, preferably 26% w/w of the dried leaf material (Kalpana, M. B.et al. “Studies on the antidiabetic activity of Ananas comosus leaves inSTZ induced diabetic rats” Der Pharmazia Lettre, 2014, 6(2), 22-30,incorporated herein by reference in its entirety).

The ethanolic pineapple leaves extract may contain, as considerableconstituents, alkaloids, flavonoids, tannins, phytosterols, glycosides,soluble carbohydrates, and phenolic compounds, but is typicallysubstantially free of saponins, diterpenes, triterpenes, andanthraquinones.

The ethanolic pineapple leaves extract may contain phenolic compounds,and in particular phenolic acids. Exemplary phenolic compounds which maybe present in the ethanolic pineapple leaves extract include, but arenot limited to, hydroxycinnamic acids such as caffeic acid andp-coumaric acid; hydroxycinnamoyl quinic acids such as chlorogenic acid,3-O-p-coumaroxylquinic acid, 4-O-p-coumaroxylquinic acid, and5-O-p-coumaroxylquinic acid; phenylpropane monoglycerides such as1-O-caffeoylglycerol, 2-O-caffeoylglycerol, 1-O-p-coumaroylglycerol,2-O-p-coumaroylglycerol, and 1-O-caffeoylglycerol; and phenylpropanediglycerides such as 1,3-O-dicaffeoylglycerol (ananasate),1,2-O-dicaffeoylglycerol, 1-O-p-coumaroyl-3-O-feruloylglycerol or itsisomers (e.g., 1-O-p-coumaroyl-2-O-feruloylglycerol or1-O-feruloyl-2-O-p-coumaroylglycerol), a mixed ester of p-coumaric acidand caffeic acid (e.g., 1-O-p-coumaroyl-3-O-caffeoylglycerol,1-O-p-coumaroyl-2-O-caffeoylglycerol or1-O-caffeoyl-2-O-p-coumaroylglycerol), a mixed ester of ferulic acid andcaffeic acid (e.g., 1-O-feruloyl-3-O-caffeoylglycerol,1-O-feruloyl-2-O-caffeoylglycerol or 1-O-caffeoyl-2-O-feruloylglycerol).

In preferred embodiments, the ethanolic pineapple leaves extract has atotal phenolic content of 15 to 50 mg, preferably 16 to 45 mg,preferably 18 to 40 mg, preferably 20 to 35 mg, preferably 21 to 30 mg,preferably about 22 mg per 100 mL of the pineapple leaves extract, asdetermined with high-performance liquid chromatography (HPLC) accordingto the method reported by Mattila et al. (Mattila, P., J. Astola, and J.Kumpulainen, “Determination of Flavonoids in Plant Material by HPLC withDiode-Array and Electro-Array Detections”, Journal of Agricultural andFood Chemistry, 2000, 48, 5834-5841).

The ethanolic pineapple leaves extract may also contain solublecarbohydrates, such as reducing sugars. In some embodiments, theethanolic pineapple leaves extract contains a reducing sugar content of3 to 7 wt. %, preferably 4 to 6 wt. %, preferably 5 to 5.5 wt. %, basedon a total weight of the extract, as measured by alkaline 3,5dinitrosalicylicacid (DNS) method (G. L. Miller., Anal. Chem., 1972,31,426, incorporated herein by reference in its entirety). Exemplaryreducing sugars which may be present in the ethanolic pineapple leavesextract may include, but are not limited to, aldohexoses such asglucose, galactose, mannose; aldopentoses such as arabinose, xylose; andhexose deoxy sugars such as fucose and rhamnose.

In some embodiments, the ethanolic pineapple leaves extract may containphytosterols such as beta-sitosterol and daucosterol.

In some embodiments, the ethanolic pineapple leaves extract describedabove may be subjected to resin column fractionation to purify andisolate certain fractions, for example, those fractions which are richin phenolic compounds (Xie, W. et al. “Hypolipidemic Mechanisms ofAnanas comosus L. Leaves in Mice: Different From Fibrates but Similar toStatins” Journal of Pharmacological Sciences, 2007, 103, 267-274; Ma,Chao et al. “Characterization of active phenolic components in theethanolic extract of Ananas comosus L. leaves using high-performanceliquid chromatography with diode array detection and tandem massspectrometry” Journal of Chromatography A, 2007, 1165(1-2), 39-44, eachincorporated herein by reference in its entirety). For example, theextraction supernatant obtained from above may be loaded onto a resincolumn preconditioned with ethanol (e.g., 95 wt. % ethanol). Then, thesupernatant of the crude extract may be eluted with distilled wateruntil no sugar was detected with a sulfuric acid-phenol colorimetricmethod. Subsequently, the column may be eluted with aqueous ethanol(e.g., 80 to 90 wt. %) and a phenolic rich fraction may be collected anddried for example under vacuum or heat. The resulting phenolic richethanolic pineapple leaves extract may have a total phenolic content of50 to 60 wt. %, preferably 52 to 58 wt. %, preferably 54 to 56 wt. %,based on a total weight of the phenolic rich ethanolic pineapple leavesextract, including the following phenolic compounds: p-coumaric acid (1to 2 wt. %, preferably 1.5 wt. %), 1-O-p-coumaroylglycerol (0.1 to 0.4wt. %, preferably 0.3 wt. %), caffeic acid (0.5 to 2 wt. %, preferably1.0 wt. %), 1-O-caffeoylglycerol (0.1 to 0.3 wt. %, preferably 0.2 wt.%) and ananasate (1,3-O-dicaffeoylglycerides) (0.05 to 0.1 wt. %,preferably 0.066 wt. %) by HPLC analysis. The phenolic rich ethanolicpineapple leaves extract may then be used in the corrosion inhibitorcompositions of the present disclosure, in the amount describedpreviously.

It should be noted that other extracts (e.g., plant extracts) such asdate palm leaf extract may be used in lieu of, or in addition to thepineapple leaves extract in the present disclosure. However, thepineapple leaves extract has been found to act synergistically with thesilver nanoparticles and the mixture of polysaccharides, and thus, inpreferred embodiments, the only extract (e.g., plant extract) present inthe corrosion inhibitor composition is the pineapple leaves extract,preferably the ethanolic pineapple leaves extract, and any of thepolysaccharides present in the mixture which can be categorized asextracts. In some embodiments, the corrosion inhibitor composition issubstantially free of date palm seed extract, date palm leaf extract,Zenthoxylum alatum plant extract, Schinopsis lorentzii extract,Aquilaria subintergra leaves extract, Rollinia occidentalis extract,Thymus algeriensis extract, Olea europaea extract (e.g., olive leavesextract), and Acalypha torta leaf extract.

In some embodiments, the corrosion inhibitor composition issubstantially free of pineapple extracts obtained from non-leaf portionsof a pineapple plant (Ananas comosus), such as pineapple stem extracts,pineapple fruit extracts, pineapple residual pulp extracts, pineapplepeel extracts, and the like. In preferred embodiments, the corrosioninhibitor composition is substantially free of pineapple leaf fibers(PALF) or pineapple hemp fibers. In some embodiments, the corrosioninhibitor composition is substantially free of bromelain.

Preferably, besides the pineapple leaves extract, no other reducingagents are present in the corrosion inhibitor compositions disclosedherein, with specific mention being made to, other plant extracts (asdescribed above, for example date palm leaf extract), microorganisms,fungi honey (e.g., mad honey), hydrazine, sodium sulfide, sodiumborohydride, trisodium citrate, and dimethyl formamide.

In preferred embodiments, the corrosion inhibitor compositions aresubstantially free of polymers other than the biopolymers of the mixtureof polysaccharides and any natural polymers present in the pineappleleaves extract, with specific mention being made to homopolymers orcopolymers of polyethylene glycol, polypropylene glycol, styrene, vinylchloride (PVC polymers), acrylonitrile-butadiene-styrene (ABS polymers),polycarbonates, (meth)acrylic acid and its salts, maleic acid (oranhydride) and its salts, styrene sulfonic acid and its salts, vinylsulfonic acid and its salts, vinylpyridine, vinylimidazole,diallylamines which cyclopolymerized to give pyrrolidine functionalgroups, allyamine, vinylamine (derivatives of vinylacetamine polymers),dimethylaminoethyl acrylate and 2-(acetoacetyl)ethyl methacrylate allylsulfonic acid and its salts, acrylamidopropyl sulfonic acid and itssalts, diallyldimethyl ammonium salts (e.g., DADMAC), diallyldi(beta-hydroxyethyl) ammonium chloride, and diallyldi(beta-ethoxyethyl) ammonium chloride, aminoalkyl acrylates such asdimethylaminoethyl acrylate, diethylaminoethyl acrylate, and7-amino-3,7-dimethyloctyl acrylate, and their salts including theiralkyl and benzyl quaternized salts; N,N′-dimethylaminopropyl acrylamideand its salts, allylamine and its salts, diallylamine and its salts,including mixtures thereof.

In preferred embodiments, the corrosion inhibitor compositions hereinare substantially free of siliceous sedimentary deposits, clays (e.g.,phyllosilicate clays), and minerals, including, but not limited to,diatomite (diatomaceous earth), bentonite, montomorrilonite, illite,bauxite, dolomite, limestone, calcite, vaterite, aragonite, magnesite,taconite, gypsum, quartz, marble, hematite, limonite, magnetite,andesite, garnet, basalt, dacite, nesosilicates or orthosilicates,sorosilicates, cyclosilicates, inosilicates, phyllosilicates,tectosilicates, kaolins, fullers earth, and halloysite.

In preferred embodiments, the corrosion inhibitor composition consistsof the aqueous alcohol base fluid, the mixture of polysaccharides(preferably carboxymethyl cellulose, gum arabic, and pectin), silvernanoparticles that are preferably formed in situ, and a pineapple leavesextract (preferably an ethanolic pineapple leaves extract).

Making the Corrosion Inhibitor Composition

One suitable method for making the corrosion inhibitor composition willnow be described, although it should be understood that many othermethods, variations, and process equipment may utilized, which aregenerally known to those of ordinary skill in the art, and the corrosioninhibitor composition may still function as intended.

Briefly, the aqueous alcohol base fluid may first be provided orprepared having an acceptable v/v ratio of water to the alcohol asdescribed above. Next each of the polysaccharides to be included may bemixed with the aqueous alcohol base fluid until complete dissolution,with optional agitation such as swirling, stirring, or sonication,thereby providing a natural polymer-base fluid solution. A silver salt,preferably a silver(I) salt, may next be added into the naturalpolymer-base fluid solution and agitated (e.g., stirred) for 10 to 30minutes, preferably 15 to 25 minutes, preferably 20 minutes to obtain asilver salt mixture.

Non-limiting examples of silver(I) salts include, but are not limitedto, silver nitrate, silver acetate, silver sulfate, silver nitrite,silver salicylate, silver carbonate, silver phosphate, and silverbenzoate, preferably silver(I) nitrate is employed. A concentration ofthe silver(I) salt in the silver salt mixture typically ranges from 0.1to 2 mM, preferably 0.2 to 1.5 mM, preferably 0.3 to 1 mM, preferably0.4 to 0.8 mM. Thereafter, the pineapple leaves extract may be added inseveral batches, or, preferably, all at once, and the resulting yellowcolor mixture may be allowed to stand at 20 to 40° C., preferably 22 to35° C., preferably 25 to 30° C. for an extended period, typically for 12to 96 hours, preferably 24 to 90 hours, preferably 36 to 80 hours,preferably 48 to 72 hours, or until a dark-yellow viscous solution isobtained signaling the complete conversion of the silver ions from thesilver(I) salt into the silver nanoparticles.

Methods of Inhibiting Corrosion

Scale deposits are formed by the precipitation and crystal growth ofsolid salts, oxides and hydroxides at a surface in contact with fluidscontaining such salts/oxides/hydroxides. In industrial fluids, such asproduced waters in oil and gas extraction, process waters in mineralprocessing, and saline water such as sea water in desalinationprocesses, alkaline earth metal cations or transition metals cations aregenerally present, including calcium, barium, and magnesium, along withtheir anion counterparts, including bicarbonate, carbonate, sulfate,phosphate, and silicate. Precipitation of these ions occurs whensolubility is exceeded either in the bulk fluid or at the interfacebetween a solid surface and the bulk fluid, or where high levels ofdissolved solids are present, and particularly at the surfaces whereheat transfer occurs such as on heat exchanger coils/pipes, autoclaves,and utility steam condensers.

Many industrial processes suffer from scale formation, with specificmention being made to desalination systems, cooling water systems,chemical process industries, mining, mineral processing, refineries,energy and geothermal, oil and gas exploration and production, utilityindustries, pulp and paper processing, food and beverage processing(e.g., molasses transport), and coal slurry transport processes. Forexample, mineral leaching equipment (e.g., carbon in leach circuits,tank leaching, carbon in pulp circuits, etc.), pressure oxidationequipment, flotation devices, thickener overflow and sedimentationbasins, oil and gas production and transportation pipelines, anddesalination heat exchange equipment are all known to experience issueswith scale buildup. Scale deposits may be of particular concern whenformed on heat transfer equipment, such as heat exchangers, autoclaves,and utility steam condensers, since scale has been shown to reduce theheat transfer efficiency of such equipment (U.S. Pat. No. 4,454,046,incorporated herein by reference in its entirety), leading to increasedcleaning costs and equipment damage and/or failure. These problemsultimately cause losses in production, increased operating costs andincreased capital equipment expenditures.

To remove scale buildup, the industry often turns to acidic treatmentfluids/pickle liquors for removing scale. However, the use of suchacidic treatments may have the unintended drawback of causing metalcorrosion.

Therefore, the present disclosure relates to a method of inhibitingcorrosion of metal during acid cleaning/pickling operations, for exampleacid cleaning/pickling operations to remove scale deposits fromdesalination equipment. The method involves treating the metal with anacidic treatment fluid that contains an acid and the corrosion inhibitorcomposition for the dual purpose of removing scale and/or other unwanteddeposits from the metal surface while simultaneously guarding that metalsurface against corrosion.

The acidic treatment fluid may be useful for removing various types ofscale including, but not limited to, calcium carbonate, calcium sulfate,calcium phosphate, barium sulfate, barium carbonate, magnesiumhydroxide, strontium sulfate, strontium carbonate, iron sulfide, ironoxides, iron carbonate, colloidal silica (polymerized silica particles),and mixtures thereof, as well as the various silicate, phosphate, and/oroxide variants of any of the above, or any scale formed from anycombination of cations and anions listed above, or any of a number ofcompounds insoluble or slightly soluble in water, with specific mentionbeing made to calcium carbonate and magnesium hydroxide scales common todesalination processes. In some embodiments, the methods herein areemployed for combating mixed scales.

Acidic Treatment Fluid

The acidic treatment fluid of the present disclosure generally containsan acid and the corrosion inhibitor composition.

The acidic treatment fluid may contain a variety of acids, preferablywater-soluble acids. Suitable acids include, but are not limited to,hydrochloric acid, formic acid, acetic acid, chloroacetic acid,hydrofluoric acid, sulfuric acid, sulfamic acid, as well as mixturesthereof, for example mud acid (mixtures of HCl and HF). In preferredembodiments, the acid is hydrochloric acid (HCl). Typically, the acidictreatment fluid contains 0.5 to 10 wt. % of the acid, preferably 1 to 5wt. % of the acid, preferably 1.5 to 4.5 wt. % of the acid, preferably 2to 4 wt. % of the acid, preferably 2.5 to 3.5 wt. % of the acid,preferably 3 wt. % of the acid, based on a total weight of the acidictreatment fluid, although more concentrated or dilute versions may alsobe used in some circumstances.

In some embodiments, the acidic treatment fluid is formed from acidifiedfresh water sources, such as distilled water, tap water, well water,purified water, or fresh water obtained from natural sources such aslakes, streams, rivers. In some embodiments, the acidic treatment fluidis formed from wastewater, which may be fresh wastewater orsalt-containing wastewater. As used herein, “wastewater” means a watersource obtained from storm drains, sedimentation ponds, runoff/outflow,landfills, as well as water sources resulting/obtained from industrialprocesses such as factories, mills, farms, mines, quarries, desalinationplants, industrial drilling operations, oil and gas recovery operations,papermaking processes, food preparation processes, phase separationprocesses, washing processes, waste treatment plants, toilet processes,power stations, incinerators, spraying and painting, or any othermanufacturing or commercial enterprise, which comprises water and one ormore compounds or materials derived from such industrial processes,including partially treated water from these sources.

In some embodiments, the acidic treatment fluid is formed from seawater(i.e., the acidic treatment fluid is acidified seawater). The acidifiedseawater may have a total dissolved solids content of, for example,30,000 to 40,000 ppm, preferably 31,000 to 39,000 ppm, preferably 32,000to 38,000 ppm, preferably 33,000 to 37,000 ppm, preferably 34,000 to36,000 ppm, preferably 35,000 ppm.

When the acidic treatment fluid contains salts, such as when acidifiedseawater is employed, representative examples of cations which may beoptionally present in the acidic treatment fluid include, but are notlimited to, sodium, potassium, magnesium, calcium, strontium, barium,iron (ferrous and ferric), lead, copper, cobalt, manganese, nickel,zinc, aluminum, chromium, and titanium, as well as mixtures thereof.Representative examples of anions which may be present in the acidictreatment fluid include, but are not limited to, chloride, carbonate,bicarbonate, sulfate, bromide, iodide, acetate, hydroxide, sulfide,hydrosulfide, chlorate, fluoride, hypochlorite, nitrate, nitrite,perchlorate, peroxide, phosphate, phosphite, sulfite, hydrogenphosphate, hydrogen sulfate, as well as mixtures thereof.

Various amounts of the corrosion inhibitor composition may be employedin the disclosed methods for effective corrosion inhibition. Typically,the corrosion inhibitor composition is present in the acidic treatmentfluid in an amount of 0.1 to 5 vol. %, preferably 0.2 to 4 vol. %,preferably 0.3 to 3 vol. %, preferably 0.4 to 2 vol. %, preferably 0.5to 1.5 vol. %, preferably 0.6 to 1.2 vol. %, preferably 0.8 to 1 vol. %,based on a total volume of the acidic treatment fluid.

The acidic treatment fluid may also optionally include one or more of anintensifier, a surfactant, a supplemental antiscalant, a supplementalcorrosion inhibitor, and an additive.

Intensifier

In some situations, for example, under particularly acidic conditions,the acidic treatment fluid may optionally further include one or moreintensifiers to further diminish the rate of corrosion. Suitableintensifiers may include, but are not limited to,

-   -   carboxylic acid compounds having 1 to 12 carbon atoms or an        ester (including protected carboxylic acid derivatives) or salt        thereof, such as formic acid, acetic acid, oxalic acid, glycolic        acid, propionic acids/esters/salts (e.g., propionic acid,        2-hydroxypropionic acid, 3-hydroxypropionic acid,        2-methoxypropionic acid, 3-methoxypropionic acid,        2-hydroxypropionic acid methyl ester, 3-hydroxypropionic acid        methyl ester, 2-methoxypropionic acid methyl ester,        3-methoxypropionic acid methyl ester, sodium        2-hydroxypropionate, sodium 3-hydroxypropionate, sodium        2-methoxypropionate, and sodium 3-methoxypropionate), lactic        acid, butanoic acid, isobutyric acid, pentanoic acid, arabinaric        acid, glucaric acid, tartaric acid, 1,1-cyclobutanedicarboxylic        acid, 2-(2-propynyl)malonic acid, 2,2-bis(hydroxymethyl)butanoic        acid, 2,2-bis(hydroxymethyl)propionic acid, 2,2-diethylmalonic        acid, 2,2-dihydroxymalonic acid hydrate,        2,2-dimethyl-1,3-dioxane-4,6-dione, 2,2-dimethylmalonic acid,        2-allylmalonic acid, 2-amino-2,4,5-trideoxypentonic acid,        2-butylmalonic acid, 2-ethylmalonic acid,        2-hydroxy-2-methylsuccinic acid, 2-isopropylmalonic acid,        2-methylmalonic acid, 2-methylserine, 3-(acryloyloxy)propanoic        acid, 3-ethoxy-2-methyl-3-oxopropanoic acid, 3-ethoxypropanoic        acid, 3-hydroxy-2-(hydroxymethyl)-2-methylpropanoic acid,        3-hydroxy-2,2-dimethylpropanoic acid, 3-hydroxy-2-oxopropanoic        acid, 3-hydroxy-3-methylbutanoic acid, 3-hydroxybutanoic acid,        3-hydroxyproline, 3-methoxy-2-methyl-3-oxopropanoic acid,        3-methoxy-3-oxopropanoic acid, 3-methoxyalanine,        3-methoxybutanoic acid, 3-methoxypropanoic acid,        3-methoxyvaline, 4-amino-3-hydroxybutanoic acid,        4-hydroxy-4-methyltetrahydro-2H-pyran-2-one,        4-methyl-5-oxotetrahydro-3-furancarboxylic acid, diethyl        malonate, dimethyl 2-ethylidenemalonate, dimethyl        2-methylmalonate, dimethyl malonate, disodium malonate, ethyl        3-ethoxypropanoate, ethyl 3-hydroxybutanoate,        hydroxydihydro-2(3H)-furanone, lithium        3-hydroxy-2-oxopropanoate, malic acid, malonic acid, methyl        2-(1-hydroxyethyl)acrylate, methyl 2-amino-3-hydroxybutanoate,        methyl 2-amino-3-hydroxypropanoate hydrochloride, methyl        2-oxo-2H-pyran-3-carboxylate, methyl 3, 3-dimethoxypropanoate,        methyl 3-hydroxy-2-(hydroxymethyl)-2-methylpropanoate, methyl        3-hydroxy-2, 2-dimethylpropanoate, methyl 3-hydroxyhexanoate,        methyl 3-methoxypropanoate, N-acetylserine, potassium        3-methoxy-3-oxopropanoate, serine, sodium 3-hydroxybutanoate,        sodium malonate dibasic monohydrate, tartronic acid, and        threonine, for example, those carboxylic        acids/esters/salts/protected derivatives described in WO        2007007025 A1—incorporated herein by reference in its entirety;    -   formates such as C₁-C₄ alkyl formates (e.g., methyl formate and        ethyl formate), aryl formates, and arylalkyl formates (e.g.,        benzyl formate);    -   formamides such as formamide, dimethyl formamide, 1,        1′-azobisformamide;    -   metal halides such as sodium chloride, sodium bromide, potassium        bromide, sodium iodide, potassium iodide, copper(I) chloride,        copper(I) iodide, copper(II) chloride, copper(II) iodide,        antimony chloride;    -   as well as combinations thereof.

When employed, the intensifier may be present in a concentration of0.001 to 3 wt. %, preferably 0.005 to 1 wt. %, preferably 0.01 to 0.5wt. %, preferably 0.05 to 0.15 wt. %, preferably 0.08 to 0.1 wt. %,based on a total weight of the acidic treatment fluid.

In some embodiments, the acidic treatment fluid is substantially free ofan intensifier.

Surfactant

The acidic treatment fluid may optionally include one or moresurfactants. Surfactants may be employed, for example, when the processequipment to be treated during the acid cleaning/pickling operation isfouled with an oily residue or coating. The surfactant(s), when present,may be included in an amount of 0.001 to 5%, preferably 0.005 to 3%,preferably 0.01 to 1%, preferably 0.1 to 0.5%, preferably 0.2 to 0.4% byweight based on a total volume of the acidic treatment fluid. Cationic,anionic, non-ionic, and/or amphoteric surfactants may be employedherein.

Cationic surfactants may include, but are not limited to

-   -   a protonated amine formed from a reaction between a C₆-C₂₆ alkyl        amine compound and an acid (e.g., acetic acid, formic acid,        propionic acid, butyric acid, pentanoic acid, hexanoic acid,        oxalic acid, malonic acid, lactic acid, glyceric acid, glycolic        acid, malic acid, citric acid, benzoic acid, p-toluenesulfonic        acid, trifluoromethanesulfonic acid, hydrochloric acid, nitric        acid, phosphoric acid, sulfuric acid, hydrobromic acid,        perchloric acid, hydroiodic acid, etc.), such as protonated        salts of C₆-C₂₆ alkyl monoamines, C₆-C₂₆ alkyl (poly)alkylene        polyamines, and alkoxylated fatty amines;    -   a protonated C₆-C₂₆ alkyl amidoamine formed from a reaction        between a C₆-C₂₆ alkyl amidoamine compound and an acid (for        example the acids listed above), such as protonated forms of the        amide reaction product between any fatty acid previously listed        (or ester derivative thereof) with a polyamine (e.g.,        putrescine, cadaverine, ethylene diamine,        N¹,N¹-dimethvlethane-1,2-diamine,        N¹,N¹-dimethylpropan-1,3-diamine,        N¹,N¹-diethylethane-1,2-diamine,        N¹,N¹-diethylpropane-1,3-diamine, spermidine,        1,1,1-tris(aminomethyl)ethane, tris(2-aminoethyl)amme, spermine,        TEPA, DETA, TETA, AEEA, PEHA, HEHA, dipropylene triamine,        tripropylene tetramine, tetrapropylene pentamine, pentapropylene        hexamine, hexapropylene heptamine, dibutylene triamine,        tributylene tetramine, tetrabutylene pentamine, pentabutylene        hexamine, hexabutylene heptamine), with specific mention being        made to protonated forms of stearamidopropyldimethylamine,        stearamidopropyldiethylamine, stearamidoethyldiethylamine,        stearamidoethyldimethylamine, palmitamidopropyldimethylamine,        palmitamidopropyldiethylamine, palmitamidoethyldiethylamine,        palmitamidoethyldimethylamine, behenamidopropyldimethylamine,        behenamidopropyldiethylmine, behenamidoethyldiethylamine,        behenamidoethyldimethylamine, arachidamidopropyldimethylamine,        arachidamidopropyldiethylamine, arachidamidoethyldiethylamine,        and arachidamidoethyldimethylamine; and    -   a quaternary ammonium compound made from alkylation with        suitable alkylating agents (e.g., dimethyl sulfate, methyl        chloride or bromide, benzyl chloride or bromide, C₆-C₂₆ alkyl        chloride or bromide, etc.) of a tertiary C₆-C₂₆ alkyl amine, an        alkoxylated (tertiary) amine, or an aprotic nitrogenous        heteroarene (optionally substituted) having at least one        aromatic nitrogen atom with a reactive lone pair of electrons,        with specific mention being made to a C₁₀-C₁₈ alkyl trimethyl        ammonium chloride or methosulfate, a di-C₁₀-C₁₈ alkyl dimethyl        ammonium chloride or methesulfate, a C₁₀-C₁₈ alkyl benzyl        dimethyl ammonium chloride, a methyl quaternized C₆-C₂₂ alkyl        propylene diamine, a methyl quaternized C₆-C₂₂ alkyl propylene        triamine, a methyl quaternized C₆-C₂₂ alkyl propylene        tetraamine, a N—C₁₀-C₁₈ alkyl pyridinium or a quinolinium        bromide or chloride such as N-octyl pyridinium bromide, N-nonyl        pyridinium bromide, N-decyl pyridinium bromide, N-dodecyl        pyridinium bromide, N-tetradecyl pyridinium bromide, N-dodecyl        pyridinium chloride, N-cyclohexyl pyridinium bromide, naphthyl        methyl quinolinium chloride, naphthyl methyl pyridinium        chloride, and cetylpyridinium chloride;    -   as well as mixtures thereof.

Anionic surfactants may include, but are not limited to:

-   -   sulfates, such as alkyl sulfates, alkyl-ester-sulfates, alkyl        ether sulfates, alkyl-alkoxy-ester-sulfate, sulfated        alkanolamides, glyceride sulfates, in particular, sulfates of        fatty alcohols or polyoxyalkylene ethers of fatty alcohols such        as sodium dodecyl sulfate, sodium laureth sulfate, ammonium        lauryl sulfate, potassium lauryl sulfate, sodium myreth sulfate;    -   sulfonates such as dodecyl benzene sulfonate, lower        alkyl-benzene sulfonates, alpha olefin sulfonates,        lignosulfonates, sulfo-carboxylic compounds;    -   phosphates of fatty alcohols or polyoxyalkylene ethers of fatty        alcohols such as cetyl phosphate salts, dicetyl phosphate salts,        ceteth-10-phosphate salts;    -   carboxylate salts of fatty acids, acylamino acids, lactylates,        and/or fatty alcohols/polyoxyalkylene ethers of fatty alcohols        such as sodium stearate, sodium behenoyl lactylate, sodium        isostearoyl lactylate, sodium caproyl lactylate, sodium        laureth-5 carboxylate, sodium laureth-6 carboxylate, sodium        laureth-11 carboxylate;    -   and mixtures thereof.

Non-ionic surfactants may include, but are not limited to:

-   -   alkanolamides of fatty acids, that is, amide reaction products        between a fatty acid and an alkanolamine compound, such as        coconut fatty acid monoethanolamide (e.g., N-methyl coco fatty        ethanol amide), coconut fatty acid diethanolamide, oleic acid        diethanolamide, and vegetable oil fatty acid diethanolamide;    -   alkoxylated alkanolamides of fatty acids, preferably ethoxylated        and/or propoxylated variants of the alkanolamides of fatty acids        using for example anywhere from 2 to 30 EO and/or PO molar        equivalents, preferably 3 to 15 EO and/or PO molar equivalents,        preferably 4 to 10 EO and/or PO molar equivalents, preferably 5        to 8 EO and/or PO molar equivalents per moles of the        alkanolamide of the fatty acid (e.g., coconut fatty acid        monoethanolamide with 4 moles of ethylene oxide);    -   amine oxides, such as N-cocoamidopropyl dimethyl amine oxide and        dimethyl C₆-C₂₂ alkyl amine oxide (e.g., dimethyl coco amine        oxide);    -   fatty esters, such as ethoxylated and/or propoxylated fatty        acids (e.g., castor oil with 2 to 40 moles of ethylene oxide),        alkoxylated glycerides (e.g., PEG-24 glyceryl monostearate),        glycol esters and derivatives, monoglycerides, polyglyceryl        esters, esters of polyalcohols, and sorbitan/sorbitol esters;    -   ethers, such as (i) alkoxylated C₁-C₂₂ alkanols, which may        include alkoxylated C₁-C₅ alkanols, preferably ethoxylated or        propoxylated C₁-C₅ alkanols (e.g., dipropylene glycol n-butyl        ether, tripropylene glycol n-butyl ether, dipropylene glycol        methyl ether, tripropylene glycol methyl ether, diethylene        glycol n-butyl ether, triethylene glycol n-butyl ether,        diethylene glycol methyl ether, triethylene glycol methyl ether)        and alkoxylated C₆-C₂₆ alkanols (including alkoxylated fatty        alcohols), preferably alkoxylated C₇-C₂₂ alkanols, more        preferably alkoxylated C₈-C₁₄ alkanols, preferably ethoxylated        or propoxylated (e.g., cetyl stearyl alcohol with 2 to 40 moles        of ethylene oxide, lauric alcohol with 2 to 40 moles of ethylene        oxide, oleic alcohol with 2 to 40 moles of ethylene oxide,        ethoxylated lanoline derivatives, laureth-3, ceteareth-6,        ceteareth-11, ceteareth-15, ceteareth-16, ceteareth-17,        ceteareth-18, ceteareth-20, ceteareth-23, ceteareth-25,        ceteareth-27, ceteareth-28, ceteareth-30, isoceteth-20,        laureth-9/myreth-9, and PPG-3 caprylyl ether); (ii) alkoxylated        polysiloxanes; (iii) ethylene oxide/propylene oxide copolymers        (e.g., PPG-1-PEG-9-lauryl glycol ether, PPG-12-buteth-16,        PPG-3-buteth-5, PPG-5-buteth-7, PPG-7-buteth-10,        PPG-9-buteth-12, PPG-12-buteth-16,

PPG-15-buteth-20, PPG-20-buteth-30, PPG-28-buteth-35, andPPG-33-buteth-45); and (iv) alkoxylated alkylphenols;

-   -   and mixtures thereof.

Amphoteric surfactants may include, but are not limited to:

-   -   C₆-C₂₂ alkyl dialkyl betaines, such as fatty dimethyl betaines        (R—N(CH₃)₂(⁺)—CH₂COO⁻), obtained from a C₆-C₂₂ alkyl dimethyl        amine which is reacted with a monohaloacetate salt (e.g., sodium        monochloroacetate), such as C₁₂-C₁₄ dimethyl betaine        (carboxylate methyl C₁₂-C₁₄ alkyl dimethylammonium);    -   C₆-C₂₂ alkyl amido betaines        (R—CO—NH—CH₂CH₂CH₂—N(CH₃)₂(⁺)—CH₂COO⁻ or        R—CO—NH—CH₂CH₂—N(CH₃)₂(⁺)—CH₂COO⁻), obtained by the reaction of        a monohaloacetate salt (e.g., sodium monochloroacetate) with the        reaction product of either dimethyl amino propylamine or        dimethyl amino ethylamine with a suitable carboxylic acid or        ester derivatives thereof, such as C₁₀-C₁₈ amidopropyl        dimethylamino betaine;    -   C₆-C₂₂ alkyl sultaines or C₆-C₂₂ alkyl amido sultaines, which        are similar to those C₆-C₂₂ alkyl dialkyl betaines or C₆-C₂₂        alkyl amido betaines described above except in which the        carboxylic group has been substituted by a sulfonic group        (R—N(CH₃)₂(⁺)—CH₂CH₂CH₂SO₃ ⁻ or        R—CO—NH—CH₂CH₂CH₂—N(CH₃)₂(⁺)—CH₂CH₂CH₂SO₃ ⁻ or        R—CO—NH—CH₂CH₂—N(CH₃)₂(⁺)—CH₂CH₂CH₂SO₃ ^(—)) or a        hydroxysulfonic group (R—N(CH₃)₂(⁺)—CH₂CH(OH)—CH₂SO₃ ⁻ or        R—CO—NH—CH₂CH₂CH₂—N(CH₃)₂(⁺)—CH₂CH(OH)—CH₂SO₃ ⁻ or        R—CO—NH—CH₂CH₂—N(CH₃)₂(⁺)—CH₂CH(OH)—CH₂SO₃ ⁻), such as C₁₀-C₁₈        dimethyl hydroxysultaine and C₁₀-C₁₈ amido propyl dimethylamino        hydroxysultaine;    -   and mixtures thereof.

In some embodiments, the acidic treatment fluid is substantially free ofa surfactant.

Supplemental Antiscalant

In some embodiments, in addition to the acid(s), the acidic treatmentfluid may also optionally include one or more supplemental antiscalants,which is a term used herein to define any substance/compound whichimparts or is expected to impart a material antiscalant or scale removaleffect when included in the acidic treatment fluid, other than the acid(e.g., HCl) present. Such supplemental antiscalants may be classified aschelants and/or dispersants, and include, but are not limited to:

-   -   phosphate esters; such as those made from blends of        polyphosphoric acid (PPA) and/or P₂O₅ with hydroxyamines, e.g.,        ethanolamine, N-methylethanolamine, N,N-dimethylethanolamine,        N-ethylethanolamine, N-propylethanolamine,        N-isopropylethanolamine, N,N-diisopropylethanolamine,        N-butylethanolamine, diethanolamine, N-methyldiethanolamine,        N-ethyldiethanolamine, triethanolamine (TEA), propanolamine        (3-Amino-1-propanol), N-methylpropanolamine,        N,N-dimethylpropanolamine, dipropanolamine, tripropanolamine,        isopropanolamine, N,N-dimethylisopropanolamine,        diisopropanolamine, triisopropanolamine,        2-amino-2-methyl-1-propanol, 2-amino-2-ethyl-1,3-propanediol,        4-amino-1-butanol, 2-amino-1-butanol, sec-butanolamine,        di-sec-butanolamine, and bishydroxyethylethylene diamine, for        example, DANOX SC-100, available from Kao, Inc., which is a 70%        by weight active composition of a phosphate ester formed from        TEA/PPA; as well as phosphate esters of PPA and/or P₂O₅ with        hydroxyamines formed by alkoxylation of a primary or secondary        amines, for example, alkoxylates of diethylenetriamine (DETA),        triethylenetetraamine (TETA), and/or tetraethylenepentaamine        (TEPA), for example as described in U.S. Pat. No.        3,477,956A—incorporated herein by reference in its entirety;    -   organic polymers, preferably polymers based on non-ionic        monomers, anionic monomers, or mixtures thereof; including, but        not limited to, polymaleates (e.g., homopolymers of maleic acid        (HPMA)), polyacrylates (e.g., acylic acid homopolymer

(PAA or HAA), sodium acrylate homopolymer), polymethacrylates,polyacrylamides, polysaccharides including modified polysaccharides(e.g., carboxymethyl inulin), amino acid-based polymers (e.g.,polyaspartic acid (PASP) homopolymer and salts thereof), polyethers(e.g., polymers based on polymerization of EO, PO, and/or BO, such asthose described in WO2015/195319A1—incorporated herein by reference inits entirety), polymers based on sulfonated monomers such as2-acrylamido-2-methylpropane sulfonic acid (AMPS), vinylsulfonates(e.g., vinylsulfonic acid and salts thereof), styrene sulfonates, etc.;including modified versions of such polymers as well as blends thereofor copolymers made from two or more types of monomers, for example,maleic acid copolymers, maleic acid terpolymers, sulfonic acidcopolymers (SPOCA), sulfonated polyacrylic acid copolymers, modifiedpolyacrylic acids, carboxylate sulfonate copolymers, acrylic acid(AA)/AMPS copolymers, AA/AMPS/non-ionic monomer terpolymers (e.g.,AA/AMPS/polyacrylamide terpolymer),carboxylate/sulfonate/maleic acid(MA) terpolymer, AA/MA copolymer (CPMA), sulfonated styrene/MAcopolymer, AA/acrylamide copolymer, AMPS/N,N-dimethylacrylamidecopolymer, phosphino carboxylic acid (PCA) polymers (e.g.,phosphinopolyacrylate), sulfonated phosphino carboxylic acid copolymer(such as BELLASOL S-50 from BWA Water Additives and DREWSPERSE 6980available from Solenis), partially hydrolyzed polyacrylamide, polyetherphosphonic acids (e.g., polyamino polyether methylene phosphonic acid(PAPEMP));

-   -   phosphonates; such as aminotris(methylenephosphonic acid)        (ATMP), phosphoisobutane tricarboxylic acid (PBTC),        1-hydroxyethylidene diphosphonic acid (HEDP),        hexamethylenediamine tetramethylene phosphonic acid (HMDT or        HMDTMPA), diethylenetriamine penta(methylenephosphonic acid)        (DTPMP), bis(hexamethylene) triamine penta (methylene        phosphonic) acid (BHPMP), bis(hexamethylene) triamine        pentabis(methylene phosphonic acid) (HMTPMP), pentaethylene        hexaamineoctakis (methylene phosphonic acid) (PEHOMP); including        aminophosphonates of ethanolamine, ammonia, ethylene diamine,        bishydroxyethylene diamine, bisaminoethylether,        diethylenetriamine, hexamethylene diamine, hyperhomologues and        isomers of hexamethylene diamine, polyamines of ethylene diamine        and diethylene tetraamine, diglycolamine and homologues, or        similar polyamines or mixtures or combinations thereof;    -   carboxylate-containing chelating agents (non-polymeric) such as        ethylene diamine tetraacetic acid (EDTA), diethylene triamine        pentaacetic acid (DPTA), hydroxyethylene diamine triacetic acid        (HEDTA), ethylene diamine di-ortho-hydroxy-phenyl acetic acid        (EDDHA), ethylene diarnine di-ortho-hydroxy-para-methyl phenyl        acetic acid (EDDHMA), ethylene diarnine        di-ortho-hydroxy-para-carboxy-phenyl acetic acid (EDDCHA),        nitrolotriacetic acid (NTA), thioglycolic acid (TGA),        hydroxyacetic acid, citric acid, tartaric acid, as well as the        sodium, potassium, and/or ammonium salts thereof;    -   including mixtures thereof.

When present, the concentration of the one or more other supplementalantiscalants in the acidic treatment fluids may be from 0.1 to 10 wt. %,preferably 0.5 to 8 wt. %, preferably 1 to 6 wt. %, preferably 2 to 4wt. %, preferably 3 wt. %, based on a total weight of the acidictreatment fluid.

Supplemental Corrosion Inhibitor

The acidic treatment fluid may also optionally include a supplementalcorrosion inhibitor, which is a term used herein to define anysubstance/compound which imparts or is expected to impart a materialanticorrosive effect when included in the acidic treatment fluid, otherthan those present in the corrosion inhibitor composition as describedabove. Therefore, the term supplemental corrosion inhibitor is meant tobe distinct and separate from the corrosion inhibitor composition andthe compounds present therein. When used, the supplemental corrosioninhibitor may be present in amounts of 0.001 to 5 wt. %, preferably 0.01to 4 wt. %, preferably 0.1 to 3 wt. %, preferably 0.5 to 2 wt. %,preferably 1 to 1.5 wt. %, based on a total weight of the acidictreatment fluid.

Any corrosion inhibitor known to those of ordinary skill in the art maybe used herein as a supplemental corrosion inhibitor. Exemplarysupplemental corrosion inhibitors include, but are not limited to,

-   -   a cinnamaldehyde compound, which are those compounds which        contain an optionally substituted aryl group separated from an        aldehyde moiety (or protecting group thereof) by one unsaturated        carbon-carbon double bond, with said aryl group being        unsubstituted (contain only hydrogen as is the case in        cinnamaldehyde) or substituted with up to 5 substituents        individually selected from the group consisting of an optionally        substituted alkyl, an optionally substituted aryl, an optionally        substituted alkoxy, an optionally substituted alkanoyloxy, a        carboxy, an optionally substituted alkoxycarbonyl, a hydroxy, a        halo, an amino group which may be unsubstituted,        monosubstituted, or disubstituted, a nitro, a cyano, a sulfate        anion, an alkylsulfate, a thiocyano, an optionally substituted        alkylthio, an optionally substituted alkylsulfonyl, an        optionally substituted arylsulfonyl, or an optionally        substituted sulfonamido (e.g., —SO₂NH₂), or wherein two adjacent        substituents together form a methylene dioxy group, with        specific mention being made to cinnamaldehyde,        phenylene)diacrylaldehyde, p-hydroxycinnamaldehyde,        p-methylcinnamaldehyde, p-ethylcinnamaldehyde,        p-methoxycinnamaldehyde, 2,4,5-trimethoxycinnamaldehyde,        3,4,5-trimethoxycinnamaldehyde, 3,4-dimethoxycinnamaldehyde,        1-ethoxy-2-acetoxycinnamaldehyde,        1-ethoxy-2-hydroxycinnamaldehyde, sinapaldehyde,        2,5-dimethoxy-3,4-methylenedioxycinnamaldehyde,        2-methoxy-4,5-methylenedioxy cinnamaldehyde, coniferyl aldehyde,        2,3-dimethoxy-4,5-methylenedioxycinnamaldehyde,        p-dimethylaminocinnamaldehyde, p-diethylaminocinnamaldehyde,        p-nitrocinnamaldehyde, o-nitrocinnamaldehyde,        3,4-methylenedioxycinnamaldehyde, sodium p-sulfocinnamaldehyde,        p-trimethylammoniumcinnamaldehyde,        p-trimethylammoniumcinnamaldehyde o-methylsulfate,        p-thiocyanocinnamaldehyde, p-chlorocinnamaldehyde,        α-methylcinnamaldehyde, β-methylcinnamaldehyde,        α-chlorocinnamaldehyde, α-bromocinnamaldehyde,        α-butylcinnamaldehyde, α-amylcinnamaldehyde,        α-hexylcinnamaldehyde, α-bromo-p-cyanocinnamaldehyde,        α-ethyl-p-methylcinnamaldehyde, and        p-methyl-a-pentylcinnamaldehyde;    -   an alkoxylated fatty amine, which are compounds having a        long-chain alkyl group made up of hydrogen and anywhere from 6        to 26 carbon atoms, preferably 8 to 22 carbon atoms, preferably        12 to 20 carbon atoms, more preferably 16 to 18 carbon atoms,        bonded to an amine functional group which is alkoxylated, where        the fatty portion may be derived/derivable from fatty acids or        fatty acid mixtures such as caprylic acid, capric acid, lauric        acid, myristic acid, palmitic acid, stearic acid, arachidic        acid, behenic acid, lignoceric acid, cerotic acid, myristoleic        acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid,        vaccenic acid, linoleic acid, linoelaidic acid, a-inolenic acid,        arachidonic acid, eicosapentaenoic acid, erucic acid,        docosahexaenoic acid, tall oil fatty acid (TOFA), coconut oil        fatty acid, tallow fatty acid, and soya fatty acid, and thus may        saturated or may contain sites of unsaturation (e.g., mono-,        di-, tri-, oligo-, or poly-unsaturated), with specific mention        being made to a coconut amine alkoxylate, a stearyl amine        alkoxylate, a palmitoleylamine alkoxylate, a oleylamine        alkoxylate, a tallow amine alkoxylate, a tall oil amine        alkoxylate, a laurylamine alkoxylate, a myristylamine        alkoxylate, a cetylamine alkoxylate, a stearylamine alkoxylate,        a linoleyl amine alkoxylate, a soya amine alkoxylate, as well as        alkoxylated ethylene diamine variants thereof, alkoxylated        trimethylene diamine variants thereof, alkoxylated diethylene        triamine variants thereof, and alkoxylated dipropylene triamine        variants thereof;    -   an imidazoline compound, which are those compounds which can be        generally formed from a reaction between (i) a fatty acid or an        ester derivative thereof, for example a C₁ to C₁₂ alkyl ester        (e.g., methyl, ethyl, etc.) of a fatty acid or a glycerol ester        of a fatty acid, and (ii) a polyamine which contains at least        one ethylene diamine group (in various molar ratios between (i)        and (ii)), such as those imidazoline compounds prepared from        reaction between (i) tall oil fatty acid (TOFA), coconut oil        fatty acid, tallow fatty acid, soya fatty acid, and/or oleic        acid and (ii) any polyamine containing two, three, four, or more        nitrogen groups, which may be primary, secondary, or tertiary        amines, so long as at least one ethylene diamine group is        present that is capable of reacting with a carboxylic acid group        to form an imidazoline structure (e.g., ethylene diamine,        β-hydroxyethyl ethylene diamine, 1,2-diaminopropane,        1,2-diaminocyclohexane, 2,3-diaminobutane,        2,3-diaminobutan-1-ol, propane-1,2,3-triamine,        tris(2-aminoethyl)amine, tetraethylenepentamine (TEPA),        diethylenetriamine (DETA), triethylentetramine (TETA),        aminoethylethanolamine (AEEA), pentaethylene hexamine (PEHA),        and hexaethylene heptamine (HEHA)), with specific mention being        made to 1:1 (molar ratio) TOFA/DETA imidazoline, 2:1 TOFA/DETA        imidazoline, 1:1 TOFA/TETA imidazoline, 2:1 TOFA/TETA        imidazol.ine, 2:1 TOFA/TETA his-imidazoline, 1:1 TOFA/TEPA        imidazoline, 2:1 TOFA/TEPA imidazoline, 2:1 TOFA/TEPA        bis-imidazoline, 3:1 TOFA/TEPA bis-imidazoline, 1:1 TOFA/AEEA        imidazoline, 2:1 TOFA/AEEA imidazoline, 1:1 TOFA/polyamine        imidazoline, 2:1 TOFA/polyamine imidazoline, 2:1 TOFA/polyamine        bis-imidazoline, 3:1 TOFA/TEPA polyamine bis-imidazoline, 1:1        Soya/DETA imidazoline, 2:1 Soya/DETA imidazoline, 1:1 Soya/TETA        imidazoline, 2:1 Soya/TETA imidazoline, 2:1 Soya/TETA        his-imidazoline, 1:1 Soya/TEPA imidazoline, 2:1 Soya/TEPA        irnidazoline, 2:1 Soya/TEPA bis-imidazoline, 3:1 TOFA/TEPA        bis-imidazoline, 1:1 Soya/AEEA imidazoline, 2:1 Soya/AEEA        imidazoline, 1:1 Soya/polyamine imidazoline, 2:1 Soya/polyamine        imidazoline, 2:1 Soya/polyamine bis-imidazoline, 1:1 Tallow/DETA        imidazoline, 2:1 Tallow/DETA imidazoline, 1:1 Tallow/TETA        imidazoline, 2:1 Tallow/TETA imidazoline, 2:1 Tallow/TETA        bis-imidazoline, 1:1 Tallow/TEPA imidazoline, 2:1 Tallow/TEPA        imidazoline. 2:1 Tallow/TEPA bis-imidazoline, 3:1 Tallow/TEPA        bis-irnidazoline, 1:1 Tallow/AEEA imidazoline, 2:1 Tallow/AEEA        imidazoline, 1:1 Tallow/polyamine imidazoline, 2:1        Tallow/polyamine imidazoline, 2:1 Tallow/polyamine        his-imidazoline, 3:1 Tallow/TEPA polyamine bis-imidazoline;    -   inorganic metal or organometallic compounds such as chromates,        arsenates, zinc salts, iodates, metavanadates, and molybdates;    -   phosphorous-containing compounds such as (poly)phosphates and        phosphonates;    -   acetylenic alcohols such as propargylic (propargyl) alcohol,        pent-4-yn-1-ol, hexynol, ethyl octynol, octynol,        3-phenyl-2-propyn-1-ol;    -   aldehydes (other than cinnamaldehydes above) such as        crotonaldehyde and aromatic aldehydes such as furfural and        p-anisaldehyde;    -   phenones including alkenyl phenone such as        β-hydroxypropiophenone, phenyl vinyl ketone, and        β-ethylphenylketocyclohexyl amino hydrochloride (including those        phenones and blends described in US20170233872A1, incorporated        herein by reference in its entirety);    -   nitrogen-containing heterocycles (other than the imidazoline and        the pyrazine corrosion inhibitors described above) such as        piperazine and hexamethylene tetramine;    -   quatemized heteroarenes (e.g., 1-(benzyl)quinolinium chloride);    -   condensation products of carbonyls and amines (e.g., Schiff        bases);    -   sulfur containing compounds such as thiocarbamides, mercapto        amino acids, esters, or peptides, thioglycols, and thioureas;    -   as well as mixtures thereof.

In preferred embodiments, the acidic treatment fluid is substantiallyfree of supplemental corrosion inhibitors.

Additives

The acidic treatment fluids may optionally further include one or moreadditives to modify the properties or functions of the acidic treatmentfluid, as needed. Typically, when present, the additive(s) may beincorporated in an amount of less than 10 wt. %, preferably less than 8wt. %, preferably less than 6 wt. %, preferably less than 4 wt. %,preferably less than 2 wt. %, preferably less than 1 wt. %, preferablyless than 0.5 wt. %, preferably less than 0.1 wt. %, based on a totalweight of the acidic treatment fluid.

Exemplary additive(s) may include, but are not limited to,

-   -   stabilizing agents e.g., polypropylene glycol, polyethylene        glycol, polysiloxane polyalkyl polyether copolymers, acrylic        copolymers, carboxyvinyl polymers, polyvinylpyrollidones,        polyacrylates;    -   dispersing agents e.g., polymeric or co-polymeric compounds of        polyacrylic acid, polyacrylic acid/maleic acid copolymers,        styrene/maleic anhydride copolymers, polymethacrylic acid, and        polyaspartic acid;    -   defoaming agents e.g., silicone oils, silicone oil emulsions,        organic defoamers, emulsions of organic defoamers,        silicone-organic emulsions, silicone-glycol compounds,        silicone/silica adducts, emulsions of silicone/silica adducts;    -   as well as mixtures thereof.

In some embodiments, the acidic treatment fluid is substantially free ofan additive.

The methods herein inhibit corrosion of metal surfaces during acidcleaning or acid pickling, preferably during acid cleaning/pickling of adesalination system. The desalination system may be used for primarydesalination (usually thermal driven process) and/or a secondarydesalination process (usually a pressure driven process involving theuse of membranes). The desalination system may be a multi-stage flash(MSF) desalination plant, a multiple effect distillation (MED) plant, avapor-compression (VC) distillation plant, a geothermal desalinationplant, a solar desalination system (e.g., multiple-effect humidification(MEH) system), or any other thermally driven desalination system knownto those of ordinary skill in the art.

Any metal surface that is susceptible to the formation of scale can betreated by the methods disclosed herein, including, but not limited to,separation vessels, pipelines, valves, spools, fittings, storage tanks,heat exchangers (e.g., coils of heat exchangers), pump parts, casings,liners, screens, and utility steam condensers, with specific mentionbeing made to the surfaces of heat exchangers (e.g., heat exchangertubes/coils) and utility steam condensers of desalination plants (e.g.,multi-stage flash desalination plant). In preferred embodiments, theacidic treatment fluid is used to remove scale from and tosimultaneously prevent corrosion of any metal parts present in/on thepart(s) being treated.

Any metal surface that may come into contact with the acidic treatmentfluid may be protected by the corrosion inhibitor composition of thepresent disclosure. Examples of such metals include, but is not limitedto, titanium and titanium alloys, carbon steels (e.g., mild steels,high-tensile steels, higher-carbon steels); high alloy steels includingchrome steels, ferritic alloy steels, austenitic stainless steels,precipitation-hardened stainless steels high nickel content steels;galvanized steel, aluminum, aluminum alloys, copper, copper nickelalloys, copper zinc alloys, brass, ferritic alloy steels, and anycombination thereof

In preferred embodiments, the metal is titanium or an alloy thereof.Titanium and titanium alloys are widely used in industry as aconstruction material for linings, vessels, piping and the like, and inparticular, for the fabrication of heat exchanger coils and utilitysteam condensers such as those commonly found in desalination plants. Insome embodiments, the metal is unalloyed titanium. In some embodiments,the metal is a titanium alloy. The titanium alloys whose corrosion canbe inhibited by the methods of the present disclosure are those alloyswhich contain titanium as the predominant metal, preferably alloyscontaining at least 50 wt. %, preferably at least 60 wt. %, preferablyat least 70 wt. %, preferably at least 80 wt. %, preferably at least 90wt. %, preferably at least 93 wt. %, preferably at least 95 wt. %,preferably at least 97 wt. %, preferably at least 99 wt. % Ti, and whichcan also include up to 30 wt. %, preferably up to 20 wt. %, preferablyup to 10 wt. %, preferably up to 7 wt. %, preferably up to 5 wt. %,preferably up to 3 wt. %, preferably up to 1 wt. %, of such other metalsas Al, V, Mo, Pd, Pt, Ni, Cr, Fe, Sn, Mn, Zr, Cb, Ta and the like. Thetitanium alloy may be an alpha alloy (e.g., Ti-5Al-2Sn-ELI,Ti-8Al-1Mo-1V), a near-alpha alloy (e.g., Ti-6Al-2Sn-4Zr-2Mo,Ti-5Al-5Sn-2Zr-2Mo, IMI 685, Ti 1100), an alpha and beta alloy (e.g.,Ti-6Al-4V, Ti-6Al-4V-ELI, Ti-6Al-6V-2Sn, Ti-6Al-7Nb), or a beta and nearbeta alloy (e.g., Ti-10V-2Fe-3Al, Ti-29Nb-13Ta-4.6Zr,[3]Ti-13V-11Cr-3Al, Ti-8Mo-8V-2Fe-3Al, Beta C, Ti-15-3). Any grade oftitanium/titanium alloy may be treated by the disclosed methods,including, but not limited to, Grade 1, Grade 2, Grade 2H, Grade 3,Grade 5, Grade 6, Grade 7, Grade 7H, Grade 9, Grade 11, Grades 13-15,Grade 16, Grade 16H, Grade 18, Grade 26H, among many others, preferablythe metal is Grade 2 titanium, which is unalloyed titanium havingstandard oxygen content.

In some embodiments, the acidic treatment fluid is pre-formed bycombining the acid (aq.), the corrosion inhibitor composition, and anyoptional components, followed by introducing the pre-formed acidictreatment fluid into an appropriate location in need of descaling, forexample, inside the heat exchanger tubing of a desalination plant. Insome embodiments, the acid (aq.) and the corrosion inhibitor composition(and any optional components) are introduced as separate streams,combining at the location to be descaled to form the acidic treatmentfluid for acid cleaning/pickling. The corrosion inhibitor compositionmay be injected before, after, or simultaneously with the acid (aq.) foruse in the acid cleaning/pickling process.

The acidic treatment fluid may be introduced for acid cleaning/picklingtreatment using any technique known to those of ordinary skill in theart. For example, the acidic treatment fluid may be injected throughsuitable injection lines to areas where acid cleaning/pickling isdesired, cycled through the plant being treated as an influent stream,or used as a soak. Treatment may be performed manually or it may beautomatic, for example, by using chemical injection pumps. In someembodiments, the acidic treatment fluid may be stored in a chemicalstorage tank and a chemical injection pump associated therewith may beused to introduce the acidic treatment fluid into the desired locationof the operation. In any of the above applications, the acidic treatmentfluid may be introduced continuously and/or in batches. The treatmentmay be carried out by using inline static mixers, inline mixers withvelocity gradient control, inline mechanical mixers with variable speedimpellers, inline jet mixers, motorized mixers, batch equipment, andappropriate chemical injection pumps and/or metering systems, just toname a few. The treatment can be automatically or manually controlled toadd any amount of the acidic treatment fluid needed for adequatedescaling/cleaning.

In some embodiments, the metal is treated with the acidic treatmentfluid under static conditions, that is, the metal (having the scaledeposit) may be in contact with a substantially stationary body of thescale inhibitor composition (e.g., soaking methods). In alternativeembodiments, the metal is treated with the acidic treatment fluid underhydrodynamic conditions, whereby the metal may be brought into contactwith the acidic treatment fluid that is in a flowing state, for example,where a stream of the acidic treatment fluid is jetted/impinged onto thesurface having the scale deposit, or where a strewn of the acidictreatment fluid is flowed or passed over the surface having the scaledeposit. For example, when the surface having the scale deposit is aninside surface of a heat exchanger coil, the acidic treatment fluid maybe flowed or passed through the heat exchanger coil in a directionsubstantially parallel to the longitudinal axis of the coil. Typically,the acidic treatment fluid may be flowed or passed over the surfacehaving the scale deposit at a flow rate of 0.1 to 10 m/s, preferably 0.5to 5 m/s, preferably 1 to 3 m/s, preferably 1.5 to 2 m/s, although flowrates above or below these ranges may also be used when appropriate.

The metal may be treated with the acidic treatment fluid at a variety oftemperatures to effect scale removal, and, even at elevatedtemperatures, the corrosion inhibitor composition present in the acidictreatment fluid remains effective at preventing corrosion from occurringto that metal surface. For example, the metal may be treated with theacidic treatment fluid at a temperature of 20 to 100° C., preferably 30to 80° C., preferably 40 to 70° C., preferably 50 to 60° C.

Corrosion rate is the speed at which metals undergo deterioration.Corrosion rate may be measured according to the American Society forTesting and Materials (ASTM) standard weight loss (immersion) test ASTMG-1 and G-4 (See ASTM-G 01-03, ASTM Book of Standards, WestConshohocken: ASTM, 2003, vol. 3.02, and ASTM-G 01-90, Standard practicefor preparing, cleaning, and evaluation corrosion test specimens, ASTMBook of Standards (Reapproved 1999), each incorporated herein byreference in its entirety, and described in the Examples), and may becomputed using millimeters per year (mm/y). In some embodiments, themethod provides a corrosion rate of less than 0.1 mm/y, preferably lessthan 0.05 mm/y, preferably less than 0.01 mm/y, preferably less than0.005 mm/y, preferably less than 0.001 mm/y, preferably less than 0.0008mm/y, preferably less than 0.0005 mm/y, when the metal is contacted withthe acidic treatment fluids for a time period of up to 200 hours,preferably up to 190 hours, preferably up to 180 hours, preferably up to170 hours, preferably up to 168 hours, at a temperature of 40 to 70° C.

Corrosion rate may also be measured using linear polarization resistance(LPR), as described in the Examples, and may be computed using milspenetration per year (mpy). In some embodiments, the method provides acorrosion rate of less than 0.6 mpy, preferably less than 0.59 mpy,preferably less than 0.58 mpy, preferably less than 0.5 mpy, preferablyless than 0.3 mpy, preferably less than 0.2 mpy, preferably less than0.1 mpy, preferably less than 0.05 mpy, preferably less than 0.01 mpy,preferably less than 0.005 mpy, preferably less than 0.001 mpy,preferably less than 0.0005 mpy, preferably less than 0.00045 mpy, whenthe metal is contacted with the acidic treatment fluids for a timeperiod of up to 36 hours, preferably up to 30 hours, preferably up to 24hours, preferably up to 20 hours, preferably up to 18 hours, preferablyup to 12 hours, at a temperature of 40 to 50° C.

The examples below are intended to further illustrate protocols forpreparing and testing the acidic treatment fluids and are not intendedto limit the scope of the claims.

Where a numerical limit or range is stated herein, the endpoints areincluded. Also, all values and subranges within a numerical limit orrange are specifically included as if explicitly written out.

As used herein the words “a” and “an” and the like carry the meaning of“one or more.”

Obviously, numerous modifications and variations of the presentinvention are possible in light of the above teachings. It is thereforeto be understood that, within the scope of the appended claims, theinvention may be practiced otherwise than as specifically describedherein.

All patents and other references mentioned above are incorporated infull herein by this reference, the same as if set forth at length.

EXAMPLES Experimental

Preparing the Pineapple Leaves Extract

A cold extraction method was used to prepare the pineapple leavesextract. Sun dried pineapple leaves were ground to powder form using anelectric blender. 5 g of the powder was soaked in 200 ml of ethanol for48 hrs with constant stirring at 800 rpm using a magnetic stirrer. Themixture was filtered and the filtrate was concentrated to a semi-solidsample using a rotary evaporator. 0.5 g of the semi-solid ethanolicextract was used in the preparation of SOLOREN B as described below.

Preparing the Corrosion Inhibitor Composition (or “formulation” or“SOLOREN B”)

Firstly, an isopropanol/distilled water mixture (50:50) was prepared.This serves as the solvent for the formulation. Secondly, 1 g each ofcarboxymethyl cellulose (CMC), gum arabic (GA), and pectin (PEC) wasaccurately weighed and dissolved in 1000 cm³ (1 L) of the solvent. Itshould be mentioned that other natural polymers like sodium alginate,chitosan, dextran, hydroxyl ethyl cellulose, soluble starch etc.(FIG. 1) could be used in place of CMC, GA, and PEC. Thirdly, thenatural polymer-solvent solution was used to prepare 1 mM of AgNO₃(i.e., 0.02 g AgNO₃ was dissolved in the solution). The mixture wasstirred for 20 minutes and thereafter, 0.5 g of ethanolic extract ofpineapple leaves (obtained as described above) was added and theresultant yellow color mixture was allowed to stand at room temperaturefor 72 h. Let it also be mentioned, that other plant extracts like thedate palm leaf extract can be used in place of the pineapple leavesextract. After 72 h, a dark-yellow viscous solution (FIG. 2), hereinreferred to as “SOLOREN B”, was obtained which signaled the completeconversion of silver ions to silver nanoparticles. See M. M. Solomon, H.Gerengi, S. A. Umoren, Carboxymethyl cellulose/silver nanoparticlescomposite: Synthesis, characterization and application as a benigncorrosion inhibitor for St37 steel in 15% H₂SO₄ medium, ACS Appl. Mater.Interfaces 9 (2017) 6376-6389; M. M. Solomon, H. Gerengi, T. Kaya, S. A.Umoren, Performance evaluation of chitosan/silver nanoparticlescomposite on St37 steel corrosion in 15% HCl solution, ACS SustainableChemistry and Engineering 5 (2017) 809-820; and M. M. Solomon, S. A.Umoren, In-situ preparation, characterisation, and anticorrosionproperty of polypropylene glycol/silver nanoparticles composite for mildsteel corrosion in acid solution. Journal of Colloid and InterfaceScience 462 (2016) 29-41, each incorporated herein by reference in theirentirety.

Materials and Instrumentation

-   -   TITANIUM GRADE 2 COMPOSITION (wt. %): C (0.10), Fe (0.30), H        (0.015), N (0.03), O (0.25), Ti (99.20).    -   ELECTROCHEMICAL WORKSTATION: Gamry Instrument        Potentiostat/Galvanostat/ZRA (Reference 600) with a Gamry        framework system based on ESA410.        Experimental Conditions    -   CONCENTRATIONS: 0.3% vol./vol, 0.4% vol./vol, and 1% vol./vol.        (% volume formulation in corrosive medium)    -   TIME: 6 h, 24 h, 72 h, 168 h    -   TEMPERATURE: 40 and 70 ° C.    -   CORROSIVE MEDIUM: Acidified seawater (2% HCl solution prepared        using seawater)    -   CORROSIVE MEDIUM CONDITION: Static and hydrodynamic    -   ROTATION SPEED EMPLOYED FOR HYDRODYNAMIC MEASUREMENTS: 600 rpm        (i.e., 1.5 m/s flow rate)        Standard Techniques Adopted    -   WEIGHT LOSS    -   LINEAR POLARIZATION RESISTANCE        Weight Loss Test

The titanium samples used for the weight loss measurements were cut into2.792 cm×3.145 cm×0.200 cm dimension (Total surface area=19.936 cm²).The surface pre-treatment of the specimens was done in accordance withthe ASTM G-1 & G-4 recommended standard. See ASTM-G 01-03, ASTM Book ofStandards, West Conshohocken: ASTM, 2003, vol. 3.02; ASTM-G 01-90,Standard practice for preparing, cleaning, and evaluation corrosion testspecimens, ASTM Book of Standards (Reapproved 1999), each incorporatedherein by reference in their entirety. The specimens were wet abradedusing silicon carbide papers (grade #400 to #800) to mirror finishing.Thereafter, they were rinsed in running water and acetone to get rid ofpossible residue generated by the abrasion process, dried using aspecimen dryer at temperature of 40° C., and then preserved in amoisture-free desiccator prior to use. Weight loss experiments werecarried out in a glass reaction vessels containing 100 mL of testsolution maintained at 40 and 70° C. respectively in a thermostatedwater bath for different immersion durations (6 h, 24 h, 72 h, and 168h). The tests were performed under total immersion in naturally aeratedand static conditions in the absence and presence of inhibitor.

Electrochemical Test

The linear polarization resistance (LPR) technique (R_(p)/E_(c) trend)was adopted for the investigation of the corrosion behavior of thetitanium grade 2 in acidified seawater without and with commercialinhibitors NEVAMINE CP-20 (“Com. A”) and PROTODIN (“Com. B”) and withinventive corrosion inhibitor SOLOREN B under static and hydrodynamicconditions. The experiments were performed using a conventional threeelectrodes Gamry Instrument Potentiostat/Galvanostat/ZRA (Reference 600)inbuilt with a Gamry framework system based on ESA410. The Gamryapplication software DC105 was used for the LPR measurements. Theprepared titanium specimen was the working electrode and has an exposedsurface area in corrosive environment of 1 cm². The counter andreference electrodes were a graphite rod and silver/silver chlorideelectrode (Ag/AgCl), respectively. The linear polarization resistanceexperiments were conducted within the potential range±0.02 V withrespect to the open circuit potential, and the current response wasmeasured at a scan rate of 0.2 mV/s. The hydrodynamic experiments weresimulated using magnetic stirrer of radius 0.023 meters. The rotationspeed adopted was 600 rpm which corresponds to a flow rate of 1.5 m/s.

Results and Discussion

The corrosion inhibitor composition described herein is environmentallyfriendly, biodegradable, cheap, readily available, easily prepared, andprovides outstanding corrosion protection performance. The inhibitor,SOLOREN B can be a replacement for the highly expensive and toxiccorrosion inhibitors currently used in heat exchanger plants and coolingwater systems. FIG. 1 shows structures of the natural polymers used orthat can be used as actives in the formulation of SOLOREN B. Theappearance of the formulation is shown in FIG. 2, though it should bementioned that SOLOREN B is colorless upon addition to the corrosivesolution. FIG. 3 shows the corrosion rate (mm/yr) recorded for titaniumgrade 2 in the absence and presence of 0.3% vol./vol of commercialinhibitors (Com. A and Com. B) or SOLOREN B at 40° C. and at differentimmersion times. A similar plot, but in the presence of 0.4% vol./vol ofcommercial inhibitors or SOLOREN B is given in FIG. 4. It is observedfrom FIGS. 3 and 4 that at 6 h the titanium specimens exhibited goodcorrosion resistance in the acid solution with and without inhibitor.The corrosion rate of the metal in the blank solution is 0.0161 mm/yrand 0.0000 mm/yr in the inhibited systems. In either case, the corrosionrate is within the acceptable corrosion rate of <0.03 mm/yr (<1 mpy) fortitanium. See M. G. Fontana, Corrosion Engineering, 3rd eds.,McGraw-Hill, 1978, p. 172; and H. Uhlig, R. Revie, Corrosion andControl, 3^(rd) ed., Wiley, 1985, p. 13, each incorporated herein byreference in their entirety. As earlier mentioned, titanium exhibitsgood corrosion resistance in acid medium. See I. N. Andijani, S. Ahmad,A. U. Malik. Corrosion behavior of titanium metal in presence ofinhibited sulfuric acid at 50° C. Presented at the InternationalDesalination Association World Congress on Desalination and Water Reuse,“The Value of Water in the 21st Century, San Diego, USA. 29 August,(1999); and I. N. Andijani, S. Ahmad, A. U. Malik, Corrosion behavior oftitanium metal in presence of inhibited sulfuric acid at 50° C.,Desalination 129 (2000) 45-51, each incorporated herein by reference intheir entirety. However, as the immersion time was increased to 24 h,the metal experienced substantial weight loss in the aggressive mediumand the calculated corrosion rate is 0.6896 mm/yr. Further inspection ofthe figures reveal that the corrosion rate slightly decreased as theimmersion time increased to 72 h. This may infer that the corrosionproduct deposited on the metal surface offers some level of protectionto the surface. By comparing the corrosion rate of the bare sample at 24h and 72 h to those of Com. A and B, it could be seen that thecommercial inhibitors decreased the corrosion rate to an extent. Forinstance, 0.3 vol. % Com. A and B decreased the corrosion rate to0.2904±0.0111 mm/yr and 0.5364±0.0008 mm/yr, respectively, after 24 h ofexposure. However, these values are higher than the acceptable corrosionrate of 0.03 mm/yr for titanium meaning that the two commercialinhibitors fails after 6 h of immersion. Clearly, it can be seen in thefigures that SOLOREN B was able to keep the corrosion rate of the metalwithin the acceptable limit up to 72 h. Thus, SOLOREN B performs farbetter than the two commercial inhibitors as a corrosion inhibitor.

Having established that SOLOREN B performed better than the twocommercial inhibitors, experiments were conducted to underscore theperformance of SOLOREN B at longer immersion time and highertemperature. FIG. 5 shows the variation of corrosion rate of titaniumgrade 2 in acidified seawater without and with 0.4% vol./vol. SOLOREN Bwith time. As can be seen in the figure, the metal corroded at analarming rate of 0.7941±0.0004 mm/yr in the unprotected acid solutionwhen the immersion time was extended to 168 h. The corrosion rate wassignificantly decreased when 0.4% vol./vol. SOLOREN B was added (i.e,0.0008±0.0001 mm/yr was recorded at 168 h). This clearly shows the higheffectiveness of SOLOREN B as a corrosion inhibitor for titanium. Again,FIG. 6 reveals that SOLOREN B is capable of inhibiting titaniumcorrosion at temperature up to 70° C. At 70° C., the presence of 0.4%vol./vol. SOLOREN B caused a decrease in the corrosion rate of the metalsample from 0.6877±0.0010 mm/yr to 0.0008±0.0002 mm/yr after 24 h ofimmersion.

To verify the weight loss results, the linear polarization resistancetechnique was used to directly measure the corrosion rate of thetitanium specimen as a function of time. The experiments were performedat 40° C. and for 24 h. The results obtained are presented in FIG. 7.The electrochemical results are in perfect agreement with the weightloss results. The commercial inhibitor (Com. A) actually protected themetal sample by decreasing the corrosion rate from about 3.6 mpy to 0.6mpy at the early stage of the measurement. This was almost sustained upto about 18,000 s but thereafter, the efficacy of the commercialinhibitor began to weaken and failed completely at about 20,730 s.SOLOREN B on the other hand, decreased the corrosion rate from 3.5 mpyto 0.5 mpy and kept the corrosion rate within the acceptable rangethroughout the time of measurement. This again shows the superiority ofSOLOREN B over the commercial inhibitor (Com. A).

SOLOREN B also performs outstandingly well under hydrodynamic condition.As can be seen in FIG. 8, without the formulation, the metal specimencorroded at an alarming rate with a corrosion rate of 8.789 mpy and4.058 mpy recorded at 45630 s and 86130 s, respectively. In the presenceof 1 vol.% SOLOREN B, the corrosion rate was kept at zero throughout theduration of measurement. In fact, at 24 h, a corrosion rate of 0.00044mpy was recorded as against 4.058 mpy for the blank.

Therefore, some of the advantages of the corrosion inhibitorcompositions include: 1) it is made from cheap raw material (the naturalpolymers are cost effective compared to the costly synthetic additivescurrently in use), 2) SOLOREN B is 100% green unlike most syntheticproducts used commercially, 3) the natural polymers as well as the plantextract used as the reducing agent are readily available, 4) SOLOREN Bdoes not require a complex procedure for formulation, 5) the naturalpolymers as well as the plant extract are biodegradable—the silvernanoparticles are present only in a minute amount and no known adverseeffect on humans or the environment has been reported 6) SOLOREN B ishighly effective at inhibiting corrosion due to the synergistic effectbetween the formulation components, and 7) reduced costs for industrieslike chemical process industry, energy and geothermal, pulp and paper,desalination industry, refineries, and utility industries in whichtitanium finds widespread usage.

The invention claimed is:
 1. A corrosion inhibitor composition,comprising: a base fluid comprising water and an alcohol; a mixture ofat least three polysaccharides selected from the group consisting ofcarboxymethyl cellulose, gum arabic, pectin, a salt of alginic acid,chitosan, dextran, hydroxyethyl cellulose, and soluble starch, with eachpolysaccharide that is present in the mixture being present in an amountof 0.05 to 0.5 wt. %, based on a total weight of the corrosion inhibitorcomposition; silver nanoparticles; and a pineapple leaves extract,wherein the corrosion inhibitor composition provides a hydrodynamiccorrosion rate of less than 0.0008 mpy on Grade-2 Ti when applied at aconcentration of 0.3-1 wt % after 168 hours of exposure to a 2% HClsolution in seawater at a temperature of 40-70° C.
 2. The corrosioninhibitor composition of claim 1, wherein the alcohol is a monoalcohol.3. The corrosion inhibitor composition of claim 1, wherein the alcoholis isopropanol.
 4. The corrosion inhibitor composition of claim 1,wherein a ratio of water to the alcohol by volume is 2:1 to 1:2.
 5. Thecorrosion inhibitor composition of claim 1, wherein threepolysaccharides are present in the mixture.
 6. The corrosion inhibitorcomposition of claim 5, wherein each of the three polysaccharides ispresent in an amount of 30 to 40 wt. %, based on a total weight of themixture.
 7. The corrosion inhibitor composition of claim 1, wherein themixture consists of carboxymethyl cellulose, gum arabic, and pectin. 8.The corrosion inhibitor composition of claim 1, wherein the silvernanoparticles are present in an amount of 0.005 to 0.1 wt. % based on atotal weight of the corrosion inhibitor composition.
 9. The corrosioninhibitor composition of claim 1, wherein the silver nanoparticles arein the form of spherical nanoparticles having an average diameter of 30to 100 nm.
 10. The corrosion inhibitor composition of claim 1, whereinthe pineapple leaves extract is an ethanolic pineapple leaves extract.11. The corrosion inhibitor composition of claim 10, wherein theethanolic pineapple leaves extract has a total phenolic content of 15 to50 mg per 100 mL of the pineapple leaves extract, as determined withhigh-performance liquid chromatography.
 12. The corrosion inhibitorcomposition of claim 1, wherein the pineapple leaves extract is presentin an amount of 0.01 to 0.1 wt. %, based on a total weight of thecorrosion inhibitor composition.
 13. The corrosion inhibitor compositionof claim 1, wherein the mixture consists of carboxymethyl cellulose, gumarabic, and pectin, and the silver nanoparticles are present in anamount of 0.005 to 0.1 wt. % based on a total weight of the corrosioninhibitor composition.
 14. The corrosion inhibitor composition of claim1, wherein the corrosion inhibitor composition consists of water,isopropanol, carboxymethyl cellulose, gum arabic, pectin, the silvernanoparticles, and the pineapple leaves extract.
 15. The corrosioninhibitor composition of claim 1, which does not contain an amine.